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Abstract:

A method of producing an organic semiconductor device is provided in
which a layer composed of an organic semiconductor having excellent
crystallinity and orientation in a low-temperature region can be formed,
and the device can be produced in the air. The method includes forming a
layer composed of an organic semiconductor precursor on a base body and
irradiating the organic semiconductor precursor with light, wherein the
organic semiconductor precursor is a porphyrin compound or an
azaporphyrin compound having in its molecule at least one of the
structure represented by the following general formula (1) or (2):
##STR00001##

Claims:

1-25. (canceled)

26. A method of producing an organic semiconductor device, comprising: an
organic semiconductor layer arrangement step of providing an organic
semiconductor layer on a gate insulating layer of a substrate on which a
gate electrode and the gate insulating layer covering the gate electrode
are arranged; and an electrode arrangement step of providing a source
electrode and a drain electrode on the organic semiconductor layer, the
organic semiconductor layer arrangement step comprising: a precursor
arrangement step of arranging a solution containing a bicyclo organic
compound which is a precursor on the gate insulating layer; a heating
step of heating the bicyclo organic compound; and a light irradiation
step of irradiating the bicyclo organic compound with light while using a
heat absorbing member, wherein a heating temperature and a heating time
in the heating step are respectively 50.degree. C. or higher and
180.degree. C. or lower and 1 second or longer and less than 30 minutes,
and wherein a main bridge of a bicycle moiety of the bicyclo organic
compound is composed of a member of the group consisting of one carbonyl
group, two carbonyl groups and a thiocarbonyl group.

Description:

[0003] The present invention relates to a novel compound and a method of
producing an organic semiconductor device.

[0004] 2. Description of the Related Art

[0005] Development of a thin film transistor using an organic
semiconductor has gradually become active since the latter half of 1980s.
In recent years, the basic performance of the thin film transistor using
the organic semiconductor has exceeded the basic performance of a thin
film transistor using amorphous silicon. Each of organic semiconductor
materials often has a high affinity for a plastic substrate on which a
semiconductor device such as a thin-film field effect transistor (FET) is
formed. Therefore, the organic semiconductor materials are each an
attractive material for a semiconductor layer in a device of which
flexibility or lightweight property is desired. In addition, some of the
organic semiconductor materials can each be formed into a film by the
application of a solution or a printing method. The use of any such
material enables a large-area device to be produced simply at a low cost.

[0006] Examples of the organic semiconductor materials heretofore proposed
include the following materials. First, the examples include acenes
disclosed in Japanese Patent Application Laid-Open No. H05-55568, such as
pentacene and tetracene. The examples further include phthalocyanines
each containing lead phthalocyanine disclosed in Japanese Patent
Application Laid-Open No. H05-190877, and low-molecular-weight compounds
such as perylene and a tetracarboxylic acid derivative of perylene. In
addition, Japanese Patent Application Laid-Open No. H08-264805 proposes
an aromatic oligomer typified by a thiophene hexamer referred to as
α-thienyl or sexithiophene, and, furthermore, polymer compounds
such as polythiophene, polythienylene vinylene, and poly-p-phenylene
vinylene. It should be noted that most of them are described in Advanced
Material, 2002, 2nd issue, p. 99 to 117.

[0007] Characteristics demanded when a device is produced by using any
such compound in the semiconductor layer of the device, such as a
non-linear optical characteristic, conductivity, and a semiconductor
characteristic, largely depend on not only the purity of the compound as
a material for the layer but also the crystallinity and orientation of
the material.

[0008] By the way, most of low-molecular-weight compounds (such as
pentacene) in each of which a π-conjugated system is expanded has high
crystallinity, and is insoluble in a solvent. Accordingly, a thin film
composed of each of those compounds is formed by employing a vacuum
deposition method in most cases. Pentacene is known to show high field
effect mobility, but has involved the following problem: pentacene is so
instable in the air as to be apt to be oxidized and to deteriorate. In
addition, when employing vacuum film formation such as a vacuum
deposition method, the merit of an organic semiconductor material is
reduced such that a large-area device can be produced from the material
at a low cost.

[0009] On the other hand, an organic semiconductor using a π-conjugated
polymer can be easily formed into a thin film by, for example, a solution
application method in many cases. Therefore, the applied development of
an organic semiconductor film using a π-conjugated polymer has been
advanced because the film is often excellent in moldability ("Japanese
Journal of Applied Physics" by the Japan Society of Applied Physics,
1991, vol. 30, p. 610 to 611). The arrangement state of molecular chains
in the π-conjugated polymer is known to have a large influence on
electrical conductivity. Similarly, it has been reported that the field
effect mobility of a π-conjugated polymer field effect transistor
greatly depends on the arrangement state of molecular chains in a
semiconductor layer ("Nature", Nature Publishing Group, 1999, vol. 401,
p. 685-687). However, the arrangement of molecular chains in the
n-conjugated polymer is performed during the period from coating with a
solution to drying of the solution, so the arrangement state of the
molecular chains may vary to a large extent owing to a change in
environment and a difference in coating method. Accordingly, the field
effect mobility varies depending on a condition under which the solution
is applied, so it may be difficult to stably produce the transistor.

[0010] In addition, in recent years, an FET has also been reported which
uses a film obtained by: forming a thin film composed of a soluble
precursor by coating; and converting the precursor into an organic
semiconductor by heat treatment or irradiation with light (J. Appl. Phys.
vol. 79, 1996, p. 2136, Japanese Patent Application Laid-Open No.
2004-266157, and Japanese Patent Application Laid-Open No. 2004-221318).
Pentacene and porphyrin have been reported as examples in which a
precursor is converted into an organic semiconductor by heat treatment.
However, problems have been raised in that the conversion of the
precursor into porphyrin or pentacene requires treatment at high
temperature, and eliminated components having large mass must be removed
by decompression. Pentacene is cited as an example in which a precursor
is converted into an organic semiconductor by irradiation with light. In
this case, treatment at high temperature is not required, but a problem
is raised in that irradiation with light must be performed in an inert
atmosphere.

[0011] Further, a dimer of pentacene is a known example of an organic
semiconductor into which a precursor can be converted with either of heat
and light. However, the dimer has involved the following problem: [4+4]
optical dimerization is employed for the dimerization of pentacene, so a
skeleton to which the dimer is adaptable is limited (Japanese Patent
Application Laid-Open No. 2004-107216).

[0012] Further, in Tetrahedron Letters 45 (2004), p. 7287 to 7289, a
material having a skeleton represented by the following general formula
(12) (hereinafter referred to as "SCO skeleton") is described as a
pentacene precursor, and it is described that the pentacene precursor is
converted into pentacene by heating. However, in Tetrahedron Letters 45
(2004), p. 7287 to 7289, it is not described that the conversion of the
pentacene precursor into pentacene proceeds also with light.

##STR00002##

[0013] In addition, in Advanced Materials 15, No. 24 (2003), p. 2066 to
2069 it is described that a pentacene precursor is converted into
pentacene by heating. However, in the document, it is described that
irradiation with light only results in the polymerization of a
substituent of the precursor, so a bicyclo skeleton is maintained, and
the conversion of the precursor into pentacene does not occur. The
foregoing indicates that an N-sulfinyl group represented by a general
formula (14) is converted with heat, but not converted with light:

##STR00003##

where R44 represents a linear or branched alkyl, alkenyl, alkoxy,
alkylthio, alkyl ester, or aryl group, a hydroxyl group, or a halogen
atom.

[0014] In addition, as reported in Organic Reactions Volume 52, in a
skeleton represented by a general formula (15), irradiation with light
results in the elimination of ketene to aromatize the remainder, but
heating at 180° C. does not cause the elimination. From those
examples, it is realized that skeletons are very rare which undergo
elimination with either of light and heat in a low-temperature process up
to 200° C.

##STR00004##

[0015] As described above, in an FET device using an organic semiconductor
compound, an organic semiconductor layer having crystallinity and
orientation has been conventionally formed through a complicated step
such as vacuum film formation.

[0016] Even the formation of a film excellent in orientation and
crystallinity by a simple method such as a coating method has often
required extremely high temperature. In addition, a film that can be
formed at low temperature has been poor in stability in the air.

SUMMARY OF THE INVENTION

[0017] That is, according to the present invention, a layer composed of an
organic semiconductor excellent in crystallinity and orientation in a
low-temperature region can be formed, and an organic semiconductor device
can be produced in the air. Accordingly, an organic semiconductor device
can be easily produced by using any one of various plastic substrates as
well as a heat-resistant substrate such as a glass substrate.

[0018] In addition, according to the present invention, an organic
semiconductor layer can be formed with either of heat and light, so a
heat process and a light process can be alternatively employed for
forming an organic semiconductor layer from one material depending on the
properties of peripheral members.

[0019] In addition, a novel compound is provided which can be used in, for
example, the afore-mentioned organic semiconductor device.

[0020] A semiconductor device obtained by a production method of the
present invention can be utilized in, for example, a plastic IC card, an
information tag, or a display because the characteristics of the device
vary to a small extent, and the device has high durability.

[0021] The present invention provides a method of producing an organic
semiconductor device having a layer composed of an organic semiconductor,
including: forming a layer composed of an organic semiconductor precursor
on a base body; and irradiating the organic semiconductor precursor with
light, wherein the layer composed of the organic semiconductor precursor
contains, as the organic semiconductor precursor, a porphyrin compound or
an azaporphyrin compound having in its molecule at least one of a
structure represented by the following general formula (1) or (2):

##STR00005##

where X1 and Y1 are each independently one selected from the
group consisting of an oxygen atom, a sulfur atom, a carbonyl group, a
thiocarbonyl group, CR1R2, and NR3, wherein R1 to
R3 are each independently one selected from the group consisting of
a hydrogen atom, linear or branched alkyl, alkenyl, alkoxy, alkylthio,
alkyl ester, and aryl groups each having 1 to 12 carbon atoms, and a
hydroxyl group, provided that both X1 and Y1 are not
CR1R2 at the same time;

##STR00006##

where X2═Y2 is represented by N═N or CR4═N
wherein R4 is one selected from the group consisting of a hydrogen
atom, linear or branched alkyl, alkenyl, alkoxy, alkylthio, alkyl ester,
and aryl groups each having 1 or more to 12 or less carbon atoms, and a
hydroxyl group.

[0022] The structure represented by the general formula (1) preferably
includes a structure represented by any one of the following general
formulae (3), (4), and (5).

##STR00007##

[0023] The organic semiconductor precursor preferably includes a compound
represented by the following general formula (9):

##STR00008##

where the B ring is represented by the following general formula (25) or
(26), R17 to R22 are each independently selected from the group
consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl
group, an alkoxy group, an alkylthio group, an ester group, an aryl
group, a heterocyclic group, and an aralkyl group, Z1 to Z4 are
each selected from the group consisting of a nitrogen atom and CR60,
and may be identical to or different from one another, R60 is
selected from the group consisting of a hydrogen atom and an aryl group
which may have a substituent, M represents two hydrogen atoms, a metal
atom, or a metal oxide, and R17 and R18, R19 and R20,
or R21 and R22 may be coupled with each other to form the B
ring;

##STR00009##

where X3 and Y3 each independently represent one selected from
the group consisting of an oxygen atom, a sulfur atom, a carbonyl group,
a thiocarbonyl group, CR68R69, and NR70, wherein R68
to R70 are each independently selected from the group consisting of
a hydrogen atom, linear or branched alkyl, alkenyl, alkoxy, alkylthio,
alkyl ester, and aryl groups each having 1 to 12 carbon atoms, and a
hydroxyl group, provided that X3 and Y3 are not
CR68R69 at the same time, R54 to R59 are each
independently selected from the group consisting of a hydrogen atom, an
alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an
aralkyl group, a phenoxy group, a cyano group, a nitro group, an ester
group, a carboxyl group, and a halogen atom, R58 and R59 may be
coupled with each other to form a five-membered heterocyclic ring or a
six-membered heterocyclic ring, and n5 and n6 are each
independently an integer of 0 or more;

##STR00010##

where X4═Y4 is represented by N═N or CR67═N,
wherein R67 is selected from the group consisting of a hydrogen
atom, linear or branched alkyl, alkenyl, alkoxy, alkylthio, alkyl ester,
and aryl groups each having 1 to 12 carbon atoms, and a hydroxyl group,
R61 to R66 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom, R65 and R66 may be coupled with each other to form a
five-membered heterocyclic ring or a six-membered heterocyclic ring, and
n7 and n8 are each independently an integer of 0 or more.

[0024] The organic semiconductor precursor preferably has a structure in
which the B ring of the general formula (9) is represented by any one of
the following general formulae (27), (28), and (29):

##STR00011##

where R54 to R59 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom, R58 and R59 may be coupled with each other to form a
five-membered heterocyclic ring or a six-membered heterocyclic ring, and
n5 and n6 are each independently an integer of 0 or more;

##STR00012##

where R71 to R76 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom, R79 and R76 may be coupled with each other to form a
five-membered heterocyclic ring or a six-membered heterocyclic ring, and
n9 and n10 are each independently an integer of 0 or more;

##STR00013##

where R77 to R82 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom, R81 and R82 may be coupled with each other to form a
five-membered heterocyclic ring or a six-membered heterocyclic ring, and
n11 and n12 are each independently an integer of 0 or more.

[0025] The organic semiconductor precursor is preferably a compound in
which all of Z1 to Z4 of the general formula (9) are each
represented by CH, and the B ring of the formula is represented by the
general formula (27).

[0026] The organic semiconductor precursor preferably includes a compound
represented by the following general formula (21):

##STR00014##

where R83 to R88 are each independently selected from the group
consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl
group, an alkoxy group, an alkylthio group, an ester group, an aryl
group, a heterocyclic group, and an aralkyl group, M4 represents two
hydrogen atoms, a metal atom, or a metal oxide, and R83 and
R84, R85 and R86, or R87 and R88 may be coupled
with each other to form a general formula (30).

##STR00015##

[0027] The irradiation of the organic semiconductor precursor with light
is preferably performed while heating the precursor.

[0028] The crystallization promoting layer preferably includes a layer
containing a polysiloxane compound.

[0029] The polysiloxane compound preferably contains a compound having at
least a structure represented by the following general formula (6):

##STR00016##

where R5 to R8 each represent any one of a substituted or
unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms, a
substituted or unsubstituted phenyl group, and a siloxane unit, R5
to R8 may be identical to or different from one another, and n
represents an integer of 1 or more.

[0030] The polysiloxane compound preferably contains a compound having at
least a structure represented by the following general formula (7) or
(8):

##STR00017##

where R9 to R12 each represent one of a substituted or
unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms, and a
substituted or unsubstituted phenyl group, R9 to R12 may be
identical to or different from one another, m and n each independently
represent an integer of 0 or more, and the sum of m and n is an integer
of 1 or more;

##STR00018##

where R13 to R16 each represent one of a substituted or
unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms, and a
substituted or unsubstituted phenyl group, R13 to R16 may be
identical to or different from one another, r and p each independently
represent an integer of 0 or more, and the sum of r and p is an integer
of 1 or more.

[0031] The organic semiconductor precursor is preferably heated by heating
the base body from the outside of the base body.

[0032] The formation of the layer composed of the organic semiconductor
precursor is preferably performed by applying or printing a solution
containing the organic semiconductor precursor on the base body.

[0033] In addition, another embodiment of the present invention is a
method for producing an organic semiconductor device having a layer
composed of an organic semiconductor, including: forming a layer composed
of an organic semiconductor precursor on a base body; and subjecting the
organic semiconductor precursor to heating and irradiation with light,
wherein the layer composed of the organic semiconductor precursor
contains, as the organic semiconductor precursor, a compound having in
its molecule at least one of a structure represented by the following
general formula (12).

##STR00019##

[0034] The layer composed of the organic semiconductor precursor is
preferably formed from a solution comprised of the compound having in its
molecule at least one of the structure represented by the general formula
(12) and an organic solvent containing at least a polar solvent.

[0035] The organic semiconductor precursor preferably includes a compound
represented by the following general formula (13):

##STR00020##

where the A ring represents one of an SCO skeleton represented by the
following general formula (12), a five-membered heterocyclic ring, and a
six-membered heterocyclic ring, R37 and R42 are each
independently selected from the group consisting of a hydrogen atom, an
alkyl group, an alkoxyl group, an ester group, and a phenyl group,
R34 to R36, R38 to R41, and R43 are each
independently selected from the group consisting of a hydrogen atom, an
alkyl group, an alkoxyl group, an aryl group, a heterocyclic group, an
aralkyl group, a phenoxy group, a cyano group, a nitro group, an ester
group, a carboxyl group, and a halogen atom, R34 to R36,
R38 to R41, and R43 may be identical to or different from
one another, R34 and R35, or R39 and R40 may be
coupled with each other to form one of an SCO skeleton, a five-membered
heterocyclic ring, and a six-membered heterocyclic ring, and the sum of
n1 to n4 represents an integer of 1 or more.

##STR00021##

[0036] The compound represented by the general formula (13) preferably
includes a compound represented by the following general formula (23).

##STR00022##

[0037] Further, still another embodiment of the present invention provides
a compound which has in its molecule at least one of a structure
represented by the following general formula (1) or (2) and has a
porphyrin skeleton or an azaporphyrin skeleton.

##STR00023##

where X1 and Y1 each independently represent one selected from
the group consisting of an oxygen atom, a sulfur atom, a carbonyl group,
a thiocarbonyl group, CR1R2, and NR3, wherein R1 to
R3 are each independently selected from the group consisting of a
hydrogen atom, linear or branched alkyl, alkenyl, alkoxy, alkylthio,
alkyl ester, and aryl groups each having 1 to 12 carbon atoms, and a
hydroxyl group, provided that X1 and Y1 are not CR1R2
at the same time;

##STR00024##

where X2═Y2 is represented by N═N or CR4═N,
and R4 is selected from the group consisting of a hydrogen atom,
linear or branched alkyl, alkenyl, alkoxy, alkylthio, alkyl ester, and
aryl groups each having 1 to 12 carbon atoms, and a hydroxyl group.

[0038] The structure represented by the general formula (1) preferably
includes a structure represented by one of the following general formulae
(3), (4), and

##STR00025##

[0039] The compound preferably has a structure represented by the
following general formula (9).

##STR00026##

where the B ring is represented by the following general formula (25) or
(26), R17 to R22 are each independently one selected from the
group consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an
alkyl group, an alkoxy group, an alkylthio group, an ester group, an aryl
group, a heterocyclic group, and an aralkyl group, Z1 to Z4 are
each selected from the group consisting of a nitrogen atom and CR60,
and may be identical to or different from one another, wherein R60
is one selected from the group consisting of a hydrogen atom and an aryl
group which may have a substituent, M represents two hydrogen atoms, a
metal atom, or a metal oxide, and each pair of R17 and R18,
R19 and R20, or R21 and R22 may be combined together
to form the B ring;

##STR00027##

where X3 and Y3 each independently represent one selected from
the group consisting of an oxygen atom, a sulfur atom, a carbonyl group,
a thiocarbonyl group, CR68R69, and NR70, R68 to
R70 are each independently one selected from the group consisting of
a hydrogen atom, linear or branched alkyl, alkenyl, alkoxy, alkylthio,
alkyl ester, and aryl groups each having 1 to 12 carbon atoms, and a
hydroxyl group, provided that X3 and Y3 are not
CR68R69 at the same time, R54 to R59 are each
independently one selected from the group consisting of a hydrogen atom,
an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an
aralkyl group, a phenoxy group, a cyano group, a nitro group, an ester
group, a carboxyl group, and a halogen atom, R58 and R59 may be
coupled with each other to form a five-membered heterocyclic ring or a
six-membered heterocyclic ring, and n5 and n6 each
independently represent an integer of 0 or more;

##STR00028##

where X4═Y4 is represented by N═N or CR67═N,
wherein R67 is one selected from the group consisting of a hydrogen
atom, linear or branched alkyl, alkenyl, alkoxy, alkylthio, alkyl ester,
and aryl groups each having 1 to 12 carbon atoms, and a hydroxyl group,
R61 to R66 are each independently one selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom, R65 and R66 may be coupled with each other to form a
five-membered heterocyclic ring or a six-membered heterocyclic ring, and
n7 and n8 each independently represent an integer of 0 or more.

[0040] The B ring of the general formula (9) preferably has a structure
represented by one of the following general formulae (27), (28), and
(29):

##STR00029##

where R54 to R59 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom, R58 and R59 may be coupled with each other to form a
five-membered heterocyclic ring or a six-membered heterocyclic ring, and
n5 and n6 each independently represent an integer of 0 or more;

##STR00030##

where R71 to R76 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom, R79 and R76 may be coupled with each other to form a
five-membered heterocyclic ring or a six-membered heterocyclic ring, and
n9 and n10 each independently represent an integer of 0 or
more;

##STR00031##

where R77 to R82 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom, R81 and R82 may be coupled with each other to form a
five-membered heterocyclic ring or a six-membered heterocyclic ring, and
n11 and n12 each independently represent an integer of 0 or
more.

[0041] All of Z1 to Z4 of the general formula (9) are preferably
represented by CH, and the B ring of the formula is preferably
represented by the general formula (27).

[0042] All of Z1 to Z4 of the general formula (9) are preferably
represented by a nitrogen atom, and the B ring of the formula is
preferably represented by the general formula (27).

[0043] The compound is preferably represented by the following general
formula (21):

##STR00032##

where R83 to R88 are each independently selected from the group
consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl
group, an alkoxy group, an alkylthio group, an ester group, an aryl
group, a heterocyclic group, and an aralkyl group, M4 represents two
hydrogen atoms, a metal atom, or a metal oxide, and R83 and
R84, R85 and R86, or R87 and R88 may be coupled
with each other to form a general formula (30).

##STR00033##

[0044] In addition, it is possible to produce a field effect transistor as
the semiconductor device.

[0045] The present invention comprehends an appropriate combination of the
above features.

[0046] Further features of the present invention will become apparent from
the following description of exemplary embodiments with reference to the
attached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

[0047] FIG. 1 is a schematic sectional view showing a structure of a top
electrode type field effect transistor in Example 1 of the present
invention.

[0048]FIG. 2 is a schematic sectional view showing a structure of a top
electrode type field effect transistor in an example of the present
invention.

[0049]FIG. 3 is a UV spectrum of an organic semiconductor film produced
in Example 24.

[0050] FIGS. 4A and 4B are NMR spectra of a compound from which an organic
semiconductor film produced in Example 23 is formed.

DESCRIPTION OF THE EMBODIMENTS

[0051] Hereinafter, the first and second embodiments of the present
invention will be described in detail.

[0052] The first embodiment of the present invention provides a method of
producing an organic semiconductor device having a layer composed of an
organic semiconductor, including: (i) forming a layer composed of an
organic semiconductor precursor on a base body; and (ii) irradiating the
organic semiconductor precursor with light; and (iii) the layer composed
of the organic semiconductor precursor contains, as the organic
semiconductor precursor, a porphyrin compound or an azaporphyrin compound
having in its molecule at least one of a structure represented by the
following general formula (1) or (2):

##STR00034##

where X1 and Y1 each independently represent one selected from
the group consisting of an oxygen atom, a sulfur atom, a carbonyl group,
a thiocarbonyl group, CR1R2, and NR3, wherein R1 to
R3 are each independently selected from the group consisting of a
hydrogen atom, linear or branched alkyl, alkenyl, alkoxy, alkylthio,
alkyl ester, and aryl groups each having 1 to 12 carbon atoms, and a
hydroxyl group, provided that X1 and Y1 are not CR1R2
at the same time;

##STR00035##

where X2═Y2 is represented by N═N or CR4═N,
and R4 is selected from the group consisting of a hydrogen atom,
linear or branched alkyl, alkenyl, alkoxy, alkylthio, alkyl ester, and
aryl groups each having 1 to 12 carbon atoms, and a hydroxyl group.

[0053] In addition, the second embodiment of the present invention
provides a compound which has in its molecule at least one of a structure
represented by the following general formula (1) or (2) and has a
porphyrin skeleton or an azaporphyrin skeleton.

[0054] Hereinafter, the respective steps possessed by the first embodiment
of the present invention, and the second embodiment of the present
invention will be described in detail.

[0055] Regarding steps (i) and (iii):

[0056] In step (i), a layer formed of an organic semiconductor precursor
is formed on a base body.

[0057] The layer composed of an organic semiconductor precursor includes
as the organic semiconductor precursor a porphyrin compound or
azaporphyrin compound having in its molecule at least one of the
structure represented by the following general formula (1) or (2):

##STR00036##

where X1 and Y1 each independently represent one selected from
an oxygen atom, a sulfur atom, a carbonyl group, a thiocarbonyl group,
CR1R2, and NR3, wherein R1 to R3 are each
independently selected from a hydrogen atom, linear or branched alkyl,
alkenyl, alkoxy, alkylthio, alkyl ester, and aryl groups that have 1 to
12 carbon atoms and may be substituted or unsubstituted, and a hydroxyl
group, provided that X1 and Y1 are not CR1R2 at the
same time. Examples of the alkyl group include a methyl group, an ethyl
group, a propyl group, an isopropyl group, a butyl group, an isobutyl
group, an s-butyl group, and a t-butyl group. Examples of the alkenyl
group include a vinyl group and an allyl group.

[0058] Examples of the alkoxy group include a methoxy group, an ethoxy
group, and a propoxy group. Examples of the alkylthio group include a
methylthio group and an ethylthio group. Examples of the alkyl ester
group include a methyl ester group, an ethyl ester group, a propyl ester
group, and a butyl ester group. Examples of the aryl group include a
phenyl group and naphthyl group that may have a substituent.

##STR00037##

where X2═Y2 is represented by N═N or CR4═N,
and R4 is selected from the group consisting of a hydrogen atom,
linear or branched alkyl, alkenyl, alkoxy, alkylthio, alkyl ester, and
aryl groups that have 1 to 12 carbon atoms and may be substituted or
unsubstituted, and a hydroxyl group. Herein, examples of the alkyl group
include a methyl group, an ethyl group, a propyl group, an isopropyl
group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl
group. Examples of the alkenyl group include a vinyl group and an allyl
group. Examples of the alkoxy group include a methoxy group, an ethoxy
group, and a propoxy group. Examples of the alkylthio group include a
methylthio group and an ethylthio group. Examples of the alkyl ester
group include a methyl ester group, an ethyl ester group, a propyl ester
group, and a butyl ester group. Examples of the aryl group include a
phenyl group and a naphthyl group that may have a substituent.

[0059] It should be noted that the term "porphyrin compound" as used in
the present invention refers to a compound having a porphyrin skeleton,
and the term "azaporphyrin compound" as used in the present invention
refers to a compound having an azaporphyrin skeleton.

[0060] In addition, the concept of the term "or" used herein includes
"and", so the phrase "A contains B or C" includes a case where A is free
from C and contains B, a case where A is free from B and contains C, and
a case where A contains B and C.

[0061] The porphyrin compound or azaporphyrin compound having a structure
represented by the general formula (1) or (2) preferably has a structure
represented by one of the following general formulae (3), (4), and (5).

##STR00038##

[0062] When an organic semiconductor precursor having as a partial
structure bicyclo skeleton represented by the general formula (1) or (2)
is irradiated with light (light is applied to the precursor), the bicyclo
skeleton undergoes a reverse Diels-Alder reaction with energy obtained by
the irradiation. Here, the term "Diels-Alder reaction" refers to an
organic chemical reaction in which a double bond referred to as a
dienophile is added to a conjugated diene to produce a cyclic structure.
The reverse Diels-Alder reaction is a reverse reaction of the Diels-Alder
reaction, i.e., a reaction in which the formed cyclic structure is
converted into a conjugated diene and dienophile. To be specific, as
shown in the following reaction formula (1) or (2), the bicyclo skeleton
is converted into an aromatic ring. In conjunction with the conversion,
the organic semiconductor precursor is changed to an organic
semiconductor.

##STR00039##

[0063] As shown in the reaction formula (1), the unit X1═Y1
is eliminated from the bicyclo skeleton represented by the general
formula (1) with light. In connection with the elimination, the bicyclo
skeleton is changed to an aromatic ring. It should be noted that when the
unit X1═Y1 is an instable structure, the unit
X1═Y1 may be further converted into a stable structure.
Accordingly, X1 and Y1 are selected depending on whether the
unit X1═Y1 can be eliminated with light. X1 and
Y1 represent at least one selected from an oxygen atom, a sulfur
atom, a carbonyl group, a thiocarbonyl group, CR1R2, and
NR3, wherein R1 to R3 each independently represent one
selected from a hydrogen atom, linear or branched alkyl, alkenyl, alkoxy,
alkylthio, alkyl ester, and aryl groups each having 1 to 12 carbon atoms,
and a hydroxyl group, provided that X1 and Y1 are not
CR1R2 at the same time. Examples of the alkyl group include a
methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl
group, an isobutyl group, an s-butyl group, and a t-butyl group. Examples
of the alkenyl group include a vinyl group and an allyl group. Examples
of the alkoxy group include a methoxy group, an ethoxy group, and a
propoxy group. Examples of the alkylthio group include a methylthio group
and an ethylthio group. Examples of the alkyl ester group include a
methyl ester group, an ethyl ester group, a propyl ester group, and a
butyl ester group. The aryl group is, for example, a phenyl group which
may have a substituent. When the number of carbon atoms of R3
exceeds 12, the molecular weight of the eliminated component increases,
so the component remains in the produced organic semiconductor in some
cases. In such cases, a sufficient semiconductor characteristic cannot be
obtained. In addition, the number of carbon atoms of R3 is more
preferably 6 or less.

##STR00040##

[0064] As shown in the reaction formula (2), the unit
X2≡Y2 is eliminated from the bicyclo skeleton represented
by the general formula (2) with light. In conjunction with the
elimination, the bicyclo skeleton is changed to an aromatic ring. It
should be noted that when the unit X2≡Y2 is an instable
structure, the unit X2≡Y2 may be further converted into a
stable structure. Accordingly, X2 and Y2 are selected depending
on whether the unit X2≡Y2 can be eliminated with light.
X2 and Y2 each preferably represent a nitrogen atom.

[0065] It should be noted that an organic semiconductor precursor having
as a partial structure an SCO skeleton represented by the general formula
(5) undergoes a reverse Diels-Alder reaction with either of heat energy
and light energy. To be specific, as shown in a reaction formula (3), the
SCO skeleton is converted into an aromatic ring. In conjunction with the
transformation, the organic semiconductor precursor is changed into an
organic semiconductor.

##STR00041##

[0066] Examples of the porphyrin compound or azaporphyrin compound having
a structure represented by the general formula (1) or (2) include
compounds represented by the following general formula (9):

##STR00042##

where: the B ring is represented by the general formula (25) or (26)
described below; R17 to R22 each are selected from a hydrogen
atom, a linear or branched alkyl group, alkenyl group, alkoxy group,
alkylthio group, alkylester group, and aryl group that are substituted or
unsubstituted and have 1 to 12 carbon atoms, a hydroxyl group, a hydrogen
atom, a heterocyclic group and an aralkyl group, and R17 to R22
are the same or different from each other; examples of the alkyl group
include a methyl group, an ethyl group, a propyl group, an isopropyl
group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl
group; examples of the alkenyl group include a vinyl group and an allyl
group; examples of the alkoxy group include a methoxy group, an ethoxy
group, and a propoxy group; examples of the alkylthio group include a
methylthio group and an ethylthio group; examples of the alkyl ester
group include a methyl ester group, an ethyl ester group, a propyl ester
group, and a butyl ester group; examples of the aryl group include a
phenyl group and naphthyl group that may have a substituent; examples of
the heterocyclic ring group include a monocylclic heterocyclic ring such
as a monovalent pyridine ring, pyradine ring, pyrimidine ring, pyridazine
ring, pyrrole ring, imidazole ring, pyrazole ring, furan ring, thiophene
ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring,
furazan ring, and selenophene ring, and silole ring that may have a
substituent, and a fused heterocyclic ring group in which a monocyclic
heterocyclic ring and an aromatic hydrocarbon ring are arbitrarily
combined and fused; examples of the aralkyl group include a benzyl group,
a phenylethyl group, and a phenethyl group; Z1 to Z4 are
selected from a nitrogen atom or CR60, and Z1 to Z4 are
the same or different from each other; R60 is selected from a
hydrogen atom and aryl groups such as a phenyl group and naphthyl group
that may have a substituent; M is not particularly limited as long as M
represents two hydrogen atoms, a metal atom, or a metal oxide; examples
of the metal include copper, gold, silver, zinc, nickel, chromium,
magnesium, and lithium. Examples of the metal oxide include TiO and VO. M
represents particularly preferably two hydrogen atoms or a copper atom;
each pair of R17 and R18, R19 and R20, and R21
and R22 are combined together to form the B ring.

##STR00043##

where X3 and Y3 each independently represent at least one
selected from the group consisting of an oxygen atom, a sulfur atom, a
carbonyl group, a thiocarbonyl group, CR68R69, and NR70,
R68 to R70 are each independently selected from the group
consisting of a hydrogen atom, linear or branched alkyl, alkenyl, alkoxy,
alkylthio, alkyl ester, and aryl groups each having 1 to 12 carbon atoms,
and a hydroxyl group, provided that X3 and Y3 are not
CR68R69 at the same time. Examples of the alkyl group include a
methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl
group, an isobutyl group, an s-butyl group, and a t-butyl group; examples
of the alkenyl group include a vinyl group and an allyl group; examples
of the alkoxy group include a methoxy group, an ethoxy group, and a
propoxy group; examples of the alkylthio group include a methylthio group
and an ethylthio group; examples of the alkyl ester group include a
methyl ester group, an ethyl ester group, a propyl ester group, and a
butyl ester group; examples of the aryl group include a phenyl group and
naphthyl group that may have a substituent. R54 to R59 are each
independently selected from the group consisting of a hydrogen atom, an
alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an
aralkyl group, a phenoxy group, a cyano group, a nitro group, an ester
group, a carboxyl group, and a halogen atom. Examples of the alkyl group
include a methyl group, an ethyl group, a propyl group, an isopropyl
group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl
group; examples of the alkoxy group include a methoxy group, an ethoxy
group, and a propoxy group; examples of the ester group include a methyl
ester group and an ethyl ester group, a propyl ester group, and a butyl
ester group; examples of the aryl group include a phenyl group and
naphthyl group that may have a substituent; examples of the heterocyclic
ring group include a monocyclic heterocyclic ring group such as a
monovalent pyridine ring, pyradine ring, pyrimidine ring, pyridazine
ring, pyrrole ring, imidazole ring, pyrazole ring, furan ring, thiophene
ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring,
furazan ring, and selenophene ring, and silole ring that may have a
substituent, and a fused heterocyclic ring group in which a monocyclic
heterocyclic ring and an aromatic hydrocarbon ring are arbitrarily
combined and fused; examples of the aralkyl group include a benzyl group,
a phenylethyl group, and a phenethyl group. R58 and R59 may be
coupled with each other to form a five-membered heterocyclic ring or a
six-membered heterocyclic ring. Herein, examples of the five-membered or
six membered heterocyclic ring include a pyridine ring, a pyradine ring,
a pyrimidine ring, a pyridazine ring, a pyrrole ring, an imidazole ring,
a pyrazole ring, a furan ring, a thiophene ring, an oxazole ring, an
isoxazole ring, a thiazole ring, an isothiazole ring, a furazan ring, a
selenophene ring, and a silole ring. n5 and n6 each
independently represent an integer of 0 or more.

##STR00044##

where X4═Y4 is represented by N═N or CR67═N,
R67 is selected from the group consisting of a hydrogen atom, linear
or branched alkyl, alkenyl, alkoxy, alkylthio, alkyl ester, and aryl
groups each having 1 to 12 carbon atoms. Herein, examples of the alkyl
group include a methyl group, an ethyl group, a propyl group, an
isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and
a t-butyl group; examples of the alkenyl group include a vinyl group and
an allyl group; examples of the alkoxy group include a methoxy group, an
ethoxy group, and a propoxy group; examples of the alkylthio group
include a methylthio group and an ethylthio group; examples of the alkyl
ester group include a methyl ester group, an ethyl ester group, a propyl
ester group, and a butyl ester group; examples of the aryl group include
a phenyl group and naphthyl group that may have a substituent. R61
to R66 are each independently selected from the group consisting of
a linear or branched alkyl group, alkoxy group, aryl group, heterocyclic
group, aralkyl group, and phenoxy group that have 1 to 12 carbon atoms
and may be substituted or unsubstituted, a cyano group, a nitro group, an
ester group, a carboxyl group, and a halogen atom. Examples of the alkyl
group include a methyl group, an ethyl group, a propyl group, an
isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and
a t-butyl group; examples of the alkoxy group include a methoxy group, an
ethoxy group, and a propoxy group; examples of the ester group include a
methyl ester group, an ethyl ester group, a propyl ester group, and a
butyl ester group; examples of the aryl group include a phenyl group and
naphthyl group that may have a substituent; examples of the heterocyclic
ring group include a monocyclic heterocyclic ring group such as a
monovalent pyridine ring, pyradine ring, pyrimidine ring, pyridazine
ring, pyrrole ring, imidazole ring, pyrazole ring, furan ring, thiophene
ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring,
furazan ring, and selenophene ring, and silole ring that may have a
substituent, and a fused heterocyclic ring group in which a monocyclic
heterocyclic ring and an aromatic hydrocarbon ring are arbitrarily
combined and fused; examples of the aralkyl group include a benzyl group,
a phenylethyl group, and a phenethyl group. R65 and R66 may be
coupled with each other to form a five-membered heterocyclic ring or a
six-membered heterocyclic ring. Examples of the five-membered or six
membered heterocyclic ring include a pyridine ring, a pyradine ring, a
pyrimidine ring, a pyridazine ring, a pyrrole ring, an imidazole ring, a
pyrazole ring, a furan ring, a thiophene ring, an oxazole ring, an
isoxazole ring, a thiazole ring, an isothiazole ring, a furazan ring, a
selenophene ring, and a silole ring. n7 and n8 each
independently represent an integer of 0 or more.

[0067] Of those structures, the B ring of the general formula (9) is
preferably a structure represented by one of the following general
formulae (27), (28), and (29) in consideration of, for example, an
influence of the remaining of components that are to be eliminated with
light on semiconductor characteristics:

##STR00045##

where R54 to R59 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom. Examples of the alkyl group include a methyl group, an ethyl group,
a propyl group, an isopropyl group, a butyl group, an isobutyl group, an
s-butyl group, and a t-butyl group; examples of the alkoxy group include
a methoxy group, an ethoxy group, and a propoxy group; examples of the
ester group include a methyl ester group, an ethyl ester group, a propyl
ester group, and a butyl ester group; examples of the aryl group include
a phenyl group and naphthyl group that may have a substituent; examples
of the heterocyclic ring group include a monocyclic heterocyclic ring
group such as a monovalent pyridine ring, pyradine ring, pyrimidine ring,
pyridazine ring, pyrrole ring, imidazole ring, pyrazole ring, furan ring,
thiophene ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole
ring, furazan ring, and selenophene ring, and silole ring that may have a
substituent, and fused heterocyclic ring group in which a monocyclic
heterocyclic ring and an aromatic hydrocarbon ring are arbitrarily
combined and fused; examples of the aralkyl group include a benzyl group,
a phenylethyl group, and a phenethyl group. R58 and R59 may be
coupled with each other to form a five-membered heterocyclic ring or a
six-membered heterocyclic ring. Examples of the five-membered or six
membered heterocyclic ring include a pyridine ring, a pyradine ring, a
pyrimidine ring, a pyridazine ring, a pyrrole ring, an imidazole ring, a
pyrazole ring, a furan ring, a thiophene ring, an oxazole ring, an
isoxazole ring, a thiazole ring, an isothiazole ring, a furazan ring, a
selenophene ring, and a silole ring. n5 and n6 each
independently represent an integer of 0 or more.

##STR00046##

where R71 to R76 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom. Examples of the alkyl group include a methyl group, an ethyl group,
a propyl group, an isopropyl group, a butyl group, an isobutyl group, an
s-butyl group, and a t-butyl group; examples of the alkoxy group include
a methoxy group, an ethoxy group, and a propoxy group; examples of the
ester group include a methyl ester group, an ethyl ester group, a propyl
ester group, and a butyl ester group; examples of the aryl group include
a phenyl group and naphthyl group that may have a substituent; examples
of the heterocyclic ring group include a monocyclic heterocyclic ring
group such as a monovalent pyridine ring, pyradine ring, pyrimidine ring,
pyridazine ring, pyrrole ring, imidazole ring, pyrazole ring, furan ring,
thiophene ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole
ring, furazan ring, and selenophene ring, and silole ring that may have a
substituent, and a fused heterocyclic ring group in which a monocyclic
heterocyclic ring and an aromatic hydrocarbon ring are arbitrarily
combined and fused; examples of the aralkyl group include a benzyl group,
a phenylethyl group, and a phenethyl group. R75 and R76 may be
coupled with each other to form a five-membered heterocyclic ring or a
six-membered heterocyclic ring. Examples of the five-membered or six
membered heterocyclic ring include a pyridine ring, a pyradine ring, a
pyrimidine ring, a pyridazine ring, a pyrrole ring, an imidazole ring, a
pyrazole ring, a furan ring, a thiophene ring, an oxazole ring, an
isoxazole ring, a thiazole ring, an isothiazole ring, a furazan ring, a
selenophene ring, and a silole ring. n9 and n10 each
independently represent an integer of 0 or more;

##STR00047##

where R77 to R82 are each independently selected from the group
consisting of a hydrogen atom, an alkyl group, an alkoxy group, an aryl
group, a heterocyclic group, an aralkyl group, a phenoxy group, a cyano
group, a nitro group, an ester group, a carboxyl group, and a halogen
atom. Examples of the alkyl group include a methyl group, an ethyl group,
a propyl group, an isopropyl group, a butyl group, an isobutyl group, an
s-butyl group, and a t-butyl group; examples of the alkoxy group include
a methoxy group, an ethoxy group, and a propoxy group; examples of the
ester group include a methyl ester group, an ethyl ester group, a propyl
ester group, and a butyl ester group; examples of the aryl group include
a phenyl group and naphthyl group that may have a substituent; examples
of the heterocyclic ring group include a monocyclic heterocyclic ring
such as a monovalent pyridine group, pyradine group, pyrimidine group,
pyridazine group, pyrrole group, imidazole group, pyrazole group, furan
group, thiophene group, oxazole group, isoxazole group, thiazole group,
isothiazole group, furazan group, and selenophene group, and silole group
that may have a substituent, and a fused heterocyclic ring group in which
a monocyclic heterocyclic ring having a single ring and an aromatic
hydrocarbon ring are arbitrarily combined and fused; examples of the
aralkyl group include a benzyl group, a phenylethyl group, and a
phenethyl group. R81 and R82 may be coupled with each other to
form a five-membered heterocyclic ring or a six-membered heterocyclic
ring. Examples of the five-membered or six membered heterocyclic ring
include a pyridine ring, a pyradine ring, a pyrimidine ring, a pyridazine
ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a furan ring, a
thiophene ring, an oxazole ring, an isoxazole ring, a thiazole ring, an
isothiazole ring, a furazan ring, a selenophene ring, and a silole ring.
n11 and n12 each independently represent an integer of 0 or
more.

[0068] Of those structures, a more preferred example includes a compound
in which all of Z1 to Z4 of the general formula (9) are
represented by CH, and the B ring of the formula is represented by the
general formula (27), or all of Z1 to Z4 of the general formula
(9) are represented by a nitrogen atom, and the B ring of the formula is
represented by the general formula (27).

[0069] A method of synthesizing those compounds is not limited, but the
compounds can be synthesized by, for example, the following synthesis
method.

[0070] A porphyrin ring in a compound in which all of Z1 to Z4
of the general formula (9) are represented by CH, and the B ring of the
formula is represented by the general formula (27) can be formed by, for
example, a method shown in reaction formulae (4) to (7), whereby a
porphyrin compound having 1 to 4 B rings can be synthesized.

##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052##

[0071] In each of the reaction formulae (4) to (7), Compound (4) having 1
to 3 B rings can be synthesized by: condensing Compound (1) and Compound
(2) in the presence of an acid catalyst such as trichloroacetic acid;
subjecting the condensate to an oxidation reaction to produce Compound
(3); forming a diol body by deprotection with an acid such as
hydrochloric acid; and subjecting the diol body to an oxidation reaction
such as Swern oxidation.

##STR00053##

[0072] As shown in the reaction formula (8), Compound (3) can be obtained
by: reducing Compound (1) to produce Compound (2); and turning Compound
(2) into a tetrameric ring in the presence of an acid catalyst. Compound
(4) having 4 B rings can be synthesized by deprotection and oxidation of
Compound (3) thus obtained.

[0073] In addition, a substituent can be introduced to a meso-position by
allowing a compound in which a hydrogen atom is present at
α-position of pyrrole, dipyrromethane, or tripyrane at the time of
a cyclization reaction to react with various aldehydes in the presence of
an acid catalyst.

[0074] In addition, when a metal is coordinated at the center of the
porphyrin ring, any method may be used, but a method involving causing a
metal acetate or the like to act on a non-metal body is preferable.

[0075] Pyrroles having various substituents at the β-positions can be
used as constitutional units of such porphyrin compound as described
above. The pyrroles having various substituents at the β-positions
can be synthesized by employing a method typified by a Barton-Zard method
or a Knorr method. In addition, a raw material for the porphyrin compound
such as dipyrromethane or tripyrane can be synthesized by appropriately
combining those pyrroles.

[0076] In addition, while there is no specific limitation concerning
methods of synthesizing pyrroles each having a group that can be
converted into the B ring, an acetonide-protected body is suitably used
as a group that can be converted into the B ring, and each pyrrole can be
synthesized by, for example, such method as shown in reaction formulae
(9) to (11).

##STR00054##

[0077] As shown in the reaction formula (9), pyrrole can be synthesized by
a Diels-Alder reaction of cyclohexadiene with bissulfonylethylene, and,
subsequently, a Barton-Zard method. In addition, a substituent at
α-position can be converted as shown in Route 1 for decarboxylation
or Route 2 for reduction.

##STR00055##

[0078] As shown in the reaction formula (10), pyrrole can be synthesized
by a Diels-Alder reaction of cyclohexadiene with benzyne, and,
subsequently, addition of PhSC1, an oxidation reaction, and a Barton-Zard
method. In addition, a substituent at α-position can be converted
as shown in Route 1 or Route 2.

##STR00056##

[0079] As shown in the reaction formula (11), Compound (4) is synthesized
by a Diels-Alder reaction of cyclohexadiene with naphthoquinone, followed
by a reaction of the resultant with a base to produce Compound (3), a
reaction of the compound with hydrazine, and treatment of the resultant
with a base for aromatization. Thereafter, pyrrole can be synthesized by
addition of PhSC1, oxidation, and, subsequently, a Barton-Zard method.
After that, a substituent at α-position can be converted as shown
in Route 1 or Route 2.

[0080] In addition, an azaporphyrin compound in which all of Z1 to
Z4 of the general formula (9) are represented by a nitrogen atom,
and the B ring of the formula is represented by the general formula (27)
can be synthesized by, for example, such method as shown in a reaction
formula (12). The method involves: turning Dicyano Compound 1 into a
tetrameric ring; and deprotecting and oxidizing the resultant to
synthesize the compound.

##STR00057##

[0081] There is no specific limitation concerning a method of synthesizing
Dicyano Compound 1 in the reaction formula (12) as a raw material for the
azaporphyrin compound, but an acetonide-protected body is suitably used
as a group that can be converted into the B ring, and the compound can be
synthesized by, for example, such method as shown in a reaction formula
(13) or (14).

##STR00058##

[0082] A nitrile compound can be synthesized by a Diels-Alder reaction of
cyclohexadiene protected by an acetonide with dicyanoacetylene.

##STR00059##

[0083] Compound 5 can be synthesized by a Diels-Alder reaction of
Acetonide-protected Cyclohexadiene 1 with Ethylene Compound 2, reduction,
and chlorination. After that, Dicyano Compound 8 can be synthesized by
synthesis of Exomethylene 6 through dehydrochlorination, a Diels-Alder
reaction of Exomethylene 6 with dicyanoacetylene, and aromatization.

[0084] The above-exemplified synthesis methods are only a few examples.
Specific examples of the structure represented by the general formula
(27) suitably used as the B ring are listed in Table 3. It should be
noted that the substituent X in the skeletons listed in the table is
selected from a hydrogen atom, a halogen atom, a cyano group, a nitro
group, a linear or branched alkyl group having 1 to 12 carbon atoms, a
phenyl group, and an ester group, and X's may be identical to or
different from each other.

[0085] Of those exemplified compounds, a structure represented by a
general formula (21) is particularly preferable.

##STR00069##

where R83 to R88 are each independently selected from the group
consisting of a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl
group, an alkoxy group, an alkylthio group, an ester group, an aryl
group, a heterocyclic group, and an aralkyl group. Examples of the alkyl
group include a methyl group, an ethyl group, a propyl group, an
isopropyl group, a butyl group, an isobutyl group, an s-butyl group, and
a t-butyl group; examples of the alkenyl group include a vinyl group and
an allyl group; examples of the alkoxy group include a methoxy group, an
ethoxy group, and a propoxy group; examples of the alkylthio group
include a methylthio group and an ethylthio group; examples of the alkyl
ester group include a methyl ester group, an ethyl ester group, a propyl
ester group, and a butyl ester group; examples of the aryl group include
a phenyl group and naphthyl group that may have a substituent; R54
to R59 each are selected independently from a hydrogen atom, an
alkyl group, an alkoxy group, an aryl group, a heterocyclic group, an
aralkyl group, a phenoxy group, a cyano group, a nitro group, an ester
group, a carboxyl group, and a halogen atom; examples of the alkyl group
include a methyl group, an ethyl group, a propyl group, an isopropyl
group, a butyl group, an isobutyl group, an s-butyl group, and a t-butyl
group; examples of the alkoxy group include a methoxy group, an ethoxy
group, and a propoxy group; examples of the ester group include a methyl
ester group, an ethyl ester group, a propyl ester group, and a butyl
ester group; examples of the aryl group include a phenyl group and
naphthyl group that may have a substituent; examples of the heterocyclic
ring group include a monocyclic heterocyclic ring such as a monovalent
pyridine ring, pyradine ring, pyrimidine ring, pyridazine ring, pyrrole
ring, imidazole ring, pyrazole ring, furan ring, thiophene ring, oxazole
ring, isoxazole ring, thiazole ring, isothiazole ring, furazan ring,
selenophene group ring, and silole ring that may have a substituent, and
a fused heterocyclic ring group in which a monocyclic heterocyclic ring
and an aromatic hydrocarbon ring are arbitrarily combined and fused;
examples of the aralkyl group include a benzyl group, a phenylethyl
group, and a phenethyl group. M4 represents two hydrogen atoms, a
metal atom, or a metal oxide. Examples of the metal include copper, gold,
silver, zinc, nickel, chromium, magnesium, and lithium. Examples of the
metal oxide include TiO and VO. M4 represents particularly preferably two
hydrogen atoms or a copper atom. Each pair of R83 and R84,
R85 and R86, or R87 and R88 may be combined together
to form a general formula (30).

##STR00070##

[0086] Preferable examples of the above-mentioned organic semiconductor
precursor to be used in the present invention are shown below.

[0087] Unsubstituted structures are primarily shown in the examples, but
the precursor may have a substituent, or a metal may coordinate at the
center of the precursor. Compounds shown here are merely examples, and
the compound of the present invention is by no means limited thereto.

[0088] Therefore, for example, the following general formula (32) can be
rewritten into a general formula (22).

[0090] It should be noted that such a compound as the present invention is
effective for solubilization of benzoporphyrin or phthalocyanine, and,
furthermore, only the portion of the compound irradiated with light can
be transformed into a photosensitizing dye, so the compound is
sufficiently expected to have, for example, an effect of reducing damage
to normal cells. Therefore, in addition to the fact that the compound can
be used in a method of producing an organic semiconductor device, the
compound may be developed into a photosensitizing dye for PDT. In
addition, such a pigment as phthalocyanine or porphyrin can be produced
by irradiation with light, so the compound has potential for application
in the field of printing where light is utilized and for forming a p-n
junction at the molecular level by irradiation with light, and may be
applied to, for example, an organic thin-film solar cell having high
sensitivity and a large area. The application of such organic
semiconductor precursor onto a base body results in the formation of a
layer composed of the organic semiconductor precursor. A method of
forming the layer composed of the organic semiconductor precursor is
preferably a method in which the organic semiconductor precursor is
dissolved in an organic solvent and applied onto the base body to form
the layer. An organic solvent to be used for dissolving the organic
semiconductor precursor is not particularly limited as long as an organic
semiconductor material neither reacts with the solvent nor precipitates.
In addition, two or more types of organic solvents may be used as a
mixture. In this case, taking into account the surface smoothness and
thickness uniformity of a coating film, it is desirable to select the
solvent.

[0091] Examples of the solvent include acetone, methylethyl ketone,
methylisobutyl ketone, cyclohexanone, hexane, heptane, cyclohexane,
tetrahydrofuran, dioxane, diethyl ether, isopropyl ether, dibutyl ether,
toluene, xylene, 1,2-dimethoxyethane, chloroform, methylene chloride,
dichloroethane, 1,2-dichloroethylene, dimethylsulfoxide, N-methyl
pyrrolidone, chlorobenzene, dichlorobenzene, and trichlorobenzene. Each
of them may be used alone as a solvent, or a mixture of two or more of
them may be used as a solvent. The concentration of a solution comprised
of the organic semiconductor precursor and the solvent, which is
arbitrarily adjusted depending on a desired thickness, is preferably 0.01
wt % or more and 5 wt % or less.

[0092] A method of applying the solution comprised of the organic
semiconductor precursor and the solvent onto the base body is not
particularly limited. Examples of the application method include the
conventional coating methods such as a spin coating method, a cast
method, a spray coating method, a doctor blade method, a die coating
method, a dipping method, a printing method, an inkjet method, and a
dropping method. In addition, examples of the printing method include
screen printing, offset printing, gravure printing, flexographic
printing, and microcontact printing. Of those application methods, the
spin coating method, the dipping method, the spray coating method, and
the inkjet method are preferable because the application amount can be
controlled so that a film having a desired thickness is formed. Further,
to prevent the intrusion of dust and the like in a coating film as much
as possible, it is desirable to filter the solution in advance by means
of a membrane filter. This is because the intrusion of insoluble matter
or dust from the outside may obstruct uniform orientation, thereby
increasing an OFF current and reduction an ON/OFF ratio. In addition, the
coating film of the organic semiconductor precursor can be subjected to
preliminary drying.

[0093] An organic semiconductor film obtained through the foregoing
operations has a thickness of preferably 10 nm or more and 500 nm or
less, or more preferably 20 nm or more and 200 nm or less. The thickness
can be measured with, for example, a surface roughness meter or a level
difference meter.

[0094] Next, in step (ii), the formed layer composed of the organic
semiconductor precursor is irradiated with light.

[0095] The irradiation of the layer composed of the organic semiconductor
precursor with light bring about such reverse Diels-Alder reaction as
shown in the reaction formulae (1) to (3), whereby a layer composed of an
organic semiconductor is formed. The wavelength of light with which the
layer composed of the organic semiconductor precursor is irradiated, is
only required to fall within an absorption wavelength region of the
organic semiconductor precursor, but preferably falls within a wavelength
region of 190 nm or more and 500 nm or less. This is because a wavelength
shorter than 190 nm may cause damage to the peripheral part of the layer
or a side reaction, and a wavelength in excess of 500 nm may cause damage
to the resultant organic semiconductor. A light source is selected from,
for example, a tungsten lamp, a halogen lamp, a metal halide lamp, a
sodium lamp, a xenon lamp, a high-pressure mercury lamp, a low-pressure
mercury lamp, and various laser light beams. A method of irradiating the
layer with light is not particularly limited as long as the organic
semiconductor precursor is converted into the organic semiconductor, but
a method of directly irradiating the organic semiconductor precursor with
light is desirable in order that a photoreaction may be more effectively
performed. It should be noted that, when heat generated by irradiation
with light is applied to the organic semiconductor precursor, the heat is
preferably cut off with a heat absorbing filter or the like. In addition,
the organic semiconductor can be patterned by irradiating the layer with
light through a mask. It is more preferable that light and heat be
simultaneously applied to the layer composed of the organic semiconductor
precursor in order that an excellent crystallized film of the organic
semiconductor may be obtained. This is because, when light energy and
heat energy are simultaneously applied to the layer, the organic
semiconductor precursor is converted into the organic semiconductor with
light, and gaps in crystal grains produced by an elimination reaction are
filled with heat energy. As a result, the layer composed of the organic
semiconductor can be led to such a more stable crystalline state that
oxygen or moisture hardly infiltrates into the layer.

[0096] In that case, heat is applied by externally heating the base body.
Any method may be employed as a heating method, but a method is
preferable in which the base body is heated on a hot plate, or in an oven
with internal air circulation or a vacuum oven. Of those, the method in
which the base body is heated on a hot plate is more preferable. The
optimum temperature at which the base body is heated varies depending on
the type of organic semiconductor precursor, but the base body is
preferably heated in the temperature region of 50° C. or higher
and 180° C. or lower in consideration of, for example, an
influence on the peripheral part of the layer.

[0097] When light and heat are simultaneously applied to the layer, the
time period for which light and heat are simultaneously applied to the
layer varies depending on, for example, the thickness and material of the
layer to a large extent, so the time period cannot be uniquely
determined. In general, however, it becomes difficult for light to
permeate into a deep portion of the crystallized film of the organic
semiconductor as the film grows, so the time period for which light
energy and heat energy are simultaneously applied to the layer is
preferably 1 second or longer and 30 minutes or shorter. In such a
manner, light can be effectively utilized in converting the organic
semiconductor precursor into the organic semiconductor. The time period
for which light energy and heat energy are simultaneously applied to the
layer is more preferably 1 minute or longer and 15 minutes or shorter. In
addition, in order that a more stable crystallized film can be obtained,
only heat energy may be further applied after simultaneously applying
light energy and heat energy.

[0098] The layer composed of the organic semiconductor obtained through
those operations has a thickness of preferably 10 nm or more and 500 nm
or less, or more preferably 20 nm or more and 200 nm or less. The
thickness can be measured with, for example, a surface roughness meter or
a level difference meter.

[0099] In the present invention, the base body is an object on which the
layer composed of the organic semiconductor precursor is to be formed.

[0100] The base body may be comprised of a single layer, or multiple
layers.

[0101] When the base body is comprised of multiple layers, the outermost
layer is preferably a crystallization promoting layer. When the outermost
layer is a crystallization promoting layer, a ground on which the
crystallization promoting layer is to be formed (in the case of a field
effect transistor, the ground is generally a structure comprised of a
support layer, a gate electrode, and a gate insulating layer; provided
that the gate insulating layer can be omitted in some cases, the
structure may be comprised only of the support layer depending on the
order in which the layers are superimposed, and other layers may be
formed) is referred to as a base material.

[0102] According to detailed investigation conducted by the inventors of
the present invention, the simultaneous application of light energy and
heat energy to the layer composed of the organic semiconductor precursor
on the crystallization promoting layer to transform the layer formed of
the organic semiconductor precursor into the layer formed of the organic
semiconductor may be important for bringing out the crystallization
promoting function to the maximum. In general, when the organic
semiconductor precursor is subjected to an elimination reaction by
applying light energy and heat energy to the precursor to produce the
organic semiconductor, the production of a gap between crystal grains
composed of the resultant compound is observed. On the other hand, when
such reaction is performed on the crystallization promoting layer, the
gap between the crystal grains of the layer composed of the organic
semiconductor is filled, whereby uniform crystals are formed over the
entire substrate.

[0103] This is probably because the crystallization promoting layer has a
function of stabilizing the crystal grains of the layer composed of the
organic semiconductor (the stabilization may involve the movement or
rotation of the grains) and promoting the junction between the crystal
grains. Therefore, the crystallization promoting layer is a layer for
stabilizing crystal grains (the stabilization may involve the movement or
rotation of the grains) and/or promoting junction between the crystal
grains.

[0104] The inventors of the present invention consider that the
crystallization promoting layer functions by virtue of an improvement in
crystallinity of the layer composed of the organic semiconductor by such
action of the crystallization promoting layer. The occurrence of the
junction between the crystal grains is considered to be particularly
preferable.

[0105] Such crystallization promoting layer is preferably a layer
containing a polysiloxane compound.

[0106] Within the scope of investigation conducted by the inventors of the
present invention, the polysiloxane compound may have an action of
promoting the crystallization of the organic semiconductor.

[0107] Further, the inventors of the present invention have found that a
method involving simultaneously applying light energy and heat energy to
the layer formed of the organic semiconductor precursor after the
application (lamination) of the layer composed of the organic
semiconductor precursor onto the surface of the layer containing the
polysiloxane compound is effective for the formation of a layer composed
of the organic semiconductor with high quality. Hereinafter, the layer
containing the polysiloxane compound may also be referred to simply as
"polysiloxane compound layer". According to such a method, organic
semiconductor crystals can be formed which, at the interface between the
layer containing the polysiloxane compound and the layer formed of the
organic semiconductor, is continuously uniform and less in defect, and
hardly deteriorates owing to external stimuli such as oxygen or water.
Accordingly, it is considered that organic semiconductor devices can be
produced in which the variation in characteristics between the devices
are small and high in durability. While such a method may be useful for
any organic semiconductor device, it is considered to be particularly
useful for the production of an organic field effect transistor which is
an example of the organic semiconductor devices.

[0108] In the present invention, the term "polysiloxane compound" refers
to a polymer having a siloxane structure (--Si--O--) and an organic
silane structure, and the term "layer composed of the polysiloxane
compound" refers to a layer composed of a polymer having a siloxane
structure (--Si--O--) and an organic silane structure. Therefore, the
polysiloxane compound may be a copolymer with any other organic or
inorganic polymer as long as the compound has the above structures. In
the case of a copolymer with any other polymer, the siloxane structure or
the organic silane structure may be present in its main chain or in its
side chain due to graft polymerization or the like. It should be noted
that the organic silane structure is a structure obtained by directly
bonding Si and C.

[0109] Possible examples of the polysiloxane compound include compounds
having various structures such as a linear structure and a cyclic
structure.

[0110] The polysiloxane compound more preferably has a highly crosslinked
or branched structure. The term "highly crosslinked or branched
structure" as used herein comprehends network, ladder-like, cage-like,
star-like, and dendritic structures. In addition, the crosslinked or
branched structure does not necessarily need to be formed through the
siloxane structure. The structure may contain a structure obtained by
crosslinking organic groups such as a vinyl group, an acryloyl group, an
epoxy group, and a cinnamoyl group, or a structure branched through an
organic group which is trifunctional or more.

[0111] Examples of the polysiloxane compound include compounds each having
a structure represented by the following general formula (6). The main
chain of such structure is a siloxane unit, and the side chains (R5
to R8) of the structure are each a substituent having an organic
group such as a hydrogen atom or a carbon atom.

##STR00081##

[0112] In the formula, R5 to R8 each represent a substituted or
unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms, a
substituted or unsubstituted phenyl group, or a siloxane unit, and
R5 to R8 may be identical to or different from one another.

[0113] Examples of the substituted alkyl group include an alkyl group in
which a hydrogen atom is substituted by a halogen atom, a hydroxyl group,
a cyano group, a phenyl group, a nitro group, a mercapto group, or a
glycidyl group. In addition, a methyl group and a methylene group may be
substituted by an amino group. Further, examples of the substituted
phenyl group include a phenyl group in which a hydrogen atom is replaced
by a halogen atom, a hydroxyl group, a cyano group, a nitro group, a
mercapto group, or a glycidyl group. Of course, the substituent is not
limited to them. It should be noted that those examples hold true for all
of R's and Rn's (n represents a natural number) in siloxane
compounds described below except for a logically improbable exception.

[0114] The substituents R5 to R8 may each independently be one
of such siloxane units as shown below:

##STR00082##

where R's are each independently a substituted or unsubstituted alkyl
group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl
group, or any one of the siloxane units shown above, and the respective
R's may be the same functional group, or may be functional groups
different from each other.

[0115] The shape of polysiloxane may include, for example, linear, cyclic,
network, ladder-like, or cage-like structures depending on the types of
substituents in the general formula (6), and polysiloxane to be used in
the present invention may take any one of these structures.

[0116] Other examples of the polysiloxane compound to be used in the
present invention include compounds each having such a structure as
represented by the following general formula (8).

##STR00083##

[0117] In the formula, R13 to R16 each represent a substituted
or unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms, or a
substituted or unsubstituted phenyl group, R13 to R16 may be
identical to or different from one another, r and p each independently
represent an integer of 0 or more, and the sum of r and p represents an
integer of 1 or more.

[0118] The polysiloxane compound to be used in the present invention
particularly preferably has at least such a specific silsesquioxane
skeleton as represented by the following general formula (7).

##STR00084##

[0119] In the formula, R9 to R12 each represent a substituted or
unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms, or a
substituted or unsubstituted phenyl group, R9 to R12 may be
identical to or different from one another, m and n each independently
represent an integer of 0 or more, and the sum of m and n represents an
integer of 1 or more. The compound may be a random copolymer or a block
copolymer. Extremely specific examples of R9 to R12 include: an
unsubstituted alkyl group such as a methyl group or an ethyl group; an
unsubstituted phenyl group; and a substituted phenyl group such as a
dimethylphenyl group or a naphthyl group. In addition, the substituents
R9 to R12 may contain various atoms such as an oxygen atom, a
nitrogen atom, and a metal atom as well as a carbon atom and a hydrogen
atom.

[0120] The silsesquioxane skeleton in the present invention will be
described. The general formula (7) shows a structure in which m repeating
silsesquioxane units each having the substituents R9 and R10
(hereinafter referred to as "first units") and n repeating silsesquioxane
units each having the substituents R11 and R12 (hereinafter
referred to as "second units") are connected to each other. m and n each
independently represent an integer of 0 or more, and m+n is an integer of
1 or more. However, the foregoing does not mean that the repetition of
the first units and the repetition of the second units are separated from
each other. Both the units may be connected to each other in a separate
manner or in a randomly intermingled manner.

[0121] In addition, a siloxane compound having both a structure
represented by the general formula (7) and a structure represented by the
general formula (8) can also be used as a polysiloxane compound in the
present invention.

[0122] As for a method of forming the crystallization promoting layer in
the present invention composed mainly of a compound having such specific
silsesquioxane skeleton as represented by the general formula (7) on the
base material, the following method is exemplified. That is, a solution
containing polyorganosilsesquioxane compounds represented by at least one
of the following general formulae (10) and (11) is applied onto the base
material and is heated and dried, whereby the base body can be obtained.

[0123] In this case, heating is carried out at a temperature of preferably
140° C. or higher and 300° C. or lower, or more preferably
150° C. or higher and 230° C. or lower. When heating is
carried out at lower than 140° C., the hydrolysis reaction of the
solution may be insufficient.

##STR00085##

[0124] In the formula, R9 and R10 each represent a substituted
or unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms, or a
substituted or unsubstituted phenyl group, R9 and R10 may be
the same functional group, R26 to R29 each independently
represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom,
and z represents an integer of 1 or more.

##STR00086##

[0125] In the formula, R11 and R12 each represent a substituted
or unsubstituted alkyl or alkenyl group having 1 to 8 carbon atoms, or a
substituted or unsubstituted phenyl group, R11 and R12 may be
the same functional group, R30 to R33 each independently
represent an alkyl group having 1 to 4 carbon atoms, or a hydrogen atom,
and y represents an integer of 1 or more.

[0126] A hydrolysis reaction is induced at the terminal of each compound
by such heating and drying, whereby the silsesquioxane compounds as raw
materials are connected to each other in ladder form so as to be
densified, provided that the temperature at which the raw material
compounds are heated and dried is not so high that organic matter
completely disappears, so the raw material compounds can be turned into
not a complete silica structure but a silsesquioxane skeleton in which
most of substituents remain.

[0127] In addition, at the time of the drying step, a small amount of an
acid such as formic acid may be added to the solution to be applied for
the purpose of aiding a reaction in which the silsesquioxane compounds as
oligomers mutually crosslink.

[0128] The addition amount of the acid is not particularly limited. When
formic acid is used as the acid, the acid is preferably added in an
amount in the range of 1 wt % to 30 wt % with respect to the solid
content weight of the polyorganosilsesquioxane compounds in the solution
to be applied because crosslinking reaction is promoted. When the
addition amount is smaller than 1 wt %, the effect of promoting
crosslinking reaction may be insufficient. In contrast, when the addition
amount is larger than 30 wt %, the properties of the film having been
dried may be impaired.

[0129] In the process of the crosslinking reaction and the removal of the
solvent of the solution, a stabilizer that does not evaporate,
volatilize, or burn off in the system is removed from the solution system
as much as possible.

[0130] Any one of arbitrary solvents including alcohols and esters can be
used as the solvent of the solution to be applied. The solvents are
selected in consideration of, for example, wettability for a substrate.

[0131] A method of applying a raw material solution for the
crystallization promoting layer onto the base material is not
particularly limited. As the application method, the conventional coating
methods can be employed, such as a spin coating method, a cast method, a
spray coating method, a doctor blade method, a die coating method, a
dipping method, a printing method, an inkjet method, and a dropping
method. Examples of the printing method include screen printing, offset
printing, gravure printing, flexographic printing, and microcontact
printing. Of those application methods, the spin coating method, the
dipping method, the spray coating method, and the inkjet method are
preferable because the application amount can be controlled so that a
film having a desired thickness is formed. In addition, it is important
that dust and the like are mixed into an application solution to the
extent possible to retain the insulation properties of the obtained film,
so it is desirable that a raw material solution be filtrated with a
membrane filter in advance.

[0132] The concentration of the solution is preferably adjusted so that
the crystallization promoting layer has a thickness of 10 nm or more. The
concentration is more preferably adjusted so that the layer has a
thickness of 15 nm or more and 500 nm or less. This is because, when the
thickness is less than 10 nm, it may become difficult to obtain a uniform
film.

[0133] Prior to the application of the raw material solution for the
crystallization promoting layer, the surface of the base material may be
modified by, for example, ultrasonic treatment with an alkali liquid or
irradiation with UV for the purpose of improving wettability of the
surface of the base material.

[0134] The organic semiconductor precursor is applied onto the base body
on which the crystallization promoting layer has been formed. Thus, the
layer composed of the organic semiconductor precursor is formed. In this
case, it is desirable that the crystallization promoting layer and the
layer composed of the organic semiconductor precursor are superimposed in
close contact with each other. The term "close contact" refers to a state
that at least part of the crystallization promoting layer and at least
part of the layer composed of the organic semiconductor precursor are in
contact with each other without the intervention of any other layer.

[0135] As described above, the layer composed of the organic semiconductor
precursor is formed on the crystallization promoting layer. After that,
the simultaneous application of light and heat results in the conversion
of a bicyclo skeleton into an aromatic ring (conversion of the precursor
into the organic semiconductor). Crystal growth due to the stacking of
organic semiconductor molecules occurs simultaneously with the conversion
into the aromatic ring, whereby the crystallized film of the organic
semiconductor is formed. Thus, the layer composed of the organic
semiconductor is formed.

[0136] FIG. 1 shows the schematic sectional view of an organic field
effect transistor where the organic field effect transistor is obtained
through the above steps. The field effect transistor shown in FIG. 1 is
made up of a gate electrode 1, an insulating layer 2, an A layer
(crystallization promoting layer) 3, a source electrode 4, a drain
electrode 5, and a B layer (layer composed of an organic semiconductor)
6.

[0137] Description is given here on the assumption that a base material is
comprised of the gate electrode 1 and the insulating layer 2, and a base
body is comprised of the gate electrode 1, the insulating layer 2, and
the A layer (crystallization promoting layer) 3.

[0138] The gate electrode 1, the source electrode 4, and the drain
electrode 5 are not particularly limited as long as they are made of
conductive materials. Examples of the materials include: platinum, gold,
silver, nickel, chromium, copper, iron, tin, antimonial lead, tantalum,
indium, aluminum, zinc, magnesium, and alloys of those metals; conductive
metal oxides such as an indium-tin oxide; and inorganic and organic
semiconductors with increased conductivity through doping and the like,
such as a silicon single crystal, polysilicon, amorphous silicon,
germanium, graphite, polyacetylene, polyparaphenylene, polythiophene,
polypyrrole, polyaniline, polythienylenevinylene, and
polyparaphenylenevinylene. Examples of a method of producing an electrode
include a sputtering method, an evaporation method, a printing method
from a solution or a paste, an inkjet method, and a dipping method. In
addition, an electrode material is preferably any of the above materials
that have low electrical resistance at a contact surface with the organic
semiconductor layer.

[0139] The insulating layer 2 is not limited as long as the A layer 3 can
be uniformly applied to the layer, but the insulating layer is preferably
one having a high dielectric constant and low conductivity. Examples of a
material for the insulating layer include: inorganic oxides and nitrides
such as silicon oxide, silicon nitride, aluminum oxide, titanium oxide,
and tantalum oxide; and polyacrylate, polymethacrylate, polyethylene
terephthalate, polyimide, and polyether. Of the above insulating
materials, an insulating material having high surface smoothness is
preferable. In addition, the A layer itself is excellent in insulating
property, and hence, the A layer itself may be used as a gate insulating
layer by adjusting the thickness of the A layer to such a thickness that
the layer exerts the insulating property.

[0140] A field effect transistor structure in the present invention may be
any one of a top contact electrode type, a bottom contact electrode type,
and a top gate electrode type. In addition, the structure is not limited
to a horizontal type structure, and may be a vertical type structure
(structure in which one of a source electrode and a drain electrode is
present on the surface of an organic semiconductor layer on the side of a
base material and the other is present on the surface of the organic
semiconductor layer on the side opposite to the base material).

[0141] The third embodiment of the present invention is a method of
producing an organic semiconductor device having a layer composed of an
organic semiconductor, including: (I) forming a layer composed of an
organic semiconductor precursor on a base body; and (II) subjecting the
organic semiconductor precursor heating and irradiating with light; and
(III) the layer composed of the organic semiconductor precursor contains,
as the organic semiconductor precursor, a compound having in its molecule
at least one of a structure represented by the following general formula
(5).

##STR00087##

[0142] The organic semiconductor precursor to be used in the present
invention contains an acene compound containing in its molecule at least
one SCO skeleton represented by the general formula (5) as a partial
structure. Such acene compound has preferably a structure represented by
a general formula (13), or more preferably a pentacene precursor.

##STR00088##

[0143] In the formula, A is a cyclic structure, and represents an SCO
skeleton represented by the general formula (12), or a five- or
six-membered heterocyclic ring. Examples of the five- or six-membered
heterocyclic ring include a pyridine ring, a pyrazine ring, a pyrimidine
ring, a pyridazine ring, a pyrrole ring, an imidazole ring, a pyrazole
ring, a furan ring, a thiophene ring, an oxazole ring, an isoxazole ring,
a thiazole ring, an isothiazole ring, a furazan ring, a selenophene ring,
and a silole ring. R37 and R42 each independently represent a
hydrogen atom, an alkyl group, an alkoxyl group, an ester group, or a
phenyl group. R34 to R36, R38 to R41, and R43
each independently represent a hydrogen atom, an alkyl group, an alkoxyl
group, an aryl group, a heterocyclic group, an aralkyl group, a phenoxy
group, a cyano group, a nitro group, an ester group, a carboxyl group, or
a halogen atom. The term "aryl group" as used herein refers to a
monovalent, monocyclic or polycyclic aromatic hydrocarbon group, and
examples of the polycyclic aromatic hydrocarbon include hydrocarbons each
obtained by condensing two to fifteen aromatic hydrocarbon rings, such as
naphthalene, anthracene, azulene, heptalene, biphenylene, indacene,
acenaphthylene, phenanthrene, triphenylene, pyrene, chrysene, picene,
perylene, pentaphene, rubicene, coronene, pyranthrene, and ovalene.
Positions at which the two to fifteen rings are condensed are not limited
to those of the examples, and the rings may be condensed at any
positions. In addition, examples of the heterocyclic ring include
monocyclic heterocyclic rings such as monovalent pyridine, pyrazine,
pyrimidine, pyridazine, pyrrole, imidazole, pyrazole, furan, thiophene,
oxazole, isoxazole, thiazole, isothiazole, furazan, selenophene, and
silole rings, and condensed heterocyclic groups each obtained by
condensing an arbitrary combination of a monocyclic heterocyclic ring and
an aromatic hydrocarbon ring. The aryl group or the heterocyclic group
may have a substituent(s), and may be substituted by the substituent(s)
at any position(s) as long as the group can be substituted by the
substituent(s) at the position(s). Further, aryl groups, heterocyclic
groups, or an aryl group and a heterocyclic group may be combined with
each other to form an oligomer. R34 to R36, R38 to
R41, and R43 may be identical to or different from one another.
Each pair of R34 and R38, and R39 and R40 may be
combined together to form an SCO skeleton, or a five- or six-membered
heterocyclic ring. Here, examples of the five- or six-membered
heterocyclic ring include a pyridine ring, a pyrazine ring, a pyrimidine
ring, a pyridazine ring, a pyrrole ring, an imidazole ring, a pyrazole
ring, a furan ring, a thiophene ring, an oxazole ring, an isoxazole ring,
a thiazole ring, an isothiazole ring, a furazan ring, a selenophene ring,
and a silole ring. The sum of n1 to n4 represents an integer of
1 or more. Of those, a structure to be converted into an acene-type
compound with light, a structure to be converted into an oligomer
obtained by coupling two to six identical or different acene-type
compounds as described above with light, or a structure to be converted
into a structure obtained by coupling the acene-type compound with a
heterocyclic ring with light is more preferable. The term "acene-type
compound" refers to a compound obtained by linearly condensing three or
more rings selected from aromatic hydrocarbon rings and heterocyclic
rings, such as anthracene, tetracene, pentacene, acridine, and
thianthrene.

[0144] Examples of a preferable compound as the organic semiconductor
precursor to be used in the present invention are shown below. It should
be noted that only a few examples are shown herein, and the compound of
the present invention is not limited to them.

##STR00089## ##STR00090## ##STR00091##

[0145] Any one of those organic semiconductor precursors is applied to the
base body in step (I), whereby the layer composed of the organic
semiconductor precursor is formed. A method of forming the layer composed
of the organic semiconductor precursor is preferably a method in which
the organic semiconductor precursor is dissolved in an organic solvent
and applied. An organic solvent to be used for dissolving the organic
semiconductor precursor is not particularly limited as long as an organic
semiconductor material neither reacts with the solvent nor precipitates.
Examples of the solvent include acetone, methylethyl ketone,
methylisobutyl ketone, cyclohexanone, hexane, heptane, cyclohexane,
tetrahydrofuran, dioxane, diethyl ether, isopropyl ether, dibutyl ether,
toluene, xylene, 1,2-dimethoxyethane, chloroform, methylene chloride,
dichloroethane, 1,2-dichloroethylene, dimethylsulfoxide, N-methyl
pyrrolidone, chlorobenzene, dichlorobenzene, and trichlorobenzene. The
concentration of the solution is arbitrarily adjusted depending on a
desired thickness, and is preferably 0.01 wt % or more and 5 wt % or
less. Taking into account the surface smoothness and thickness uniformity
of a coating film, a solvent is desirably selected. In addition, two or
more kinds of organic solvents may be used as a mixture, and a polar
solvent is particularly preferably mixed in the mixture. This is because
the mixing of the polar solvent is expected to alleviate orientation
resulting from the dipole of the SCO skeleton to lead the skeleton to a
better orientation state, whereby the semiconductor characteristic of the
precursor improves, though the reason for the expectation is unclear.
Examples of the polar solvent to be mixed include nitrile-, ester-,
alcohol-, and cyclic ether-type solvents such as acetonitrile, ethyl
acetate, acetone, methyl ethyl ketone, acetylacetone, tetrahydrofuran,
dioxane, methanol, ethanol, n-propanol, isopropanol, n-butanol, and
N-methylpyrrolidone. Of those, an alcohol-type solvent such as methanol,
ethanol, 1-propanol, isopropanol, or n-butanol is particularly preferably
mixed. The ratio at which the polar solvent is mixed, which is not
particularly limited as long as the organic semiconductor precursor
neither reacts with the solvent nor precipitates, is preferably such that
the molar ratio of the organic semiconductor precursor and the polar
solvent (polar solvent/organic semiconductor precursor) is 2 or more and
30 or less.

[0146] A method of forming layer composed of the organic semiconductor
precursor is not particularly limited. The formation method is performed
by means of any one of the conventional coating methods such as a spin
coating method, a cast method, a spray coating method, a doctor blade
method, a die coating method, a dipping method, a printing method, an
inkjet method, and a dropping method. Examples of the printing method
include screen printing, offset printing, gravure printing, flexographic
printing, and microcontact printing. Of those application methods, the
spin coating method, the dipping method, the spray coating method, and
the inkjet method are preferable because the application amount can be
controlled so that a film having a desired thickness is formed. To
prevent the intrusion of dust and the like in a coating film as much as
possible, it is desirable to filter the solution in advance by means of a
membrane filter. This is because the intrusion of insoluble matter or
dust from the outside may obstruct uniform orientation, thereby
increasing an OFF current and reducing an ON/OFF ratio. In addition, the
coating film of the organic semiconductor precursor can be subjected to
preliminary drying.

[0147] The layer formed of the organic semiconductor precursor thus formed
is heated or irradiated with light in step (II), whereby such reverse
Diels-Alder reaction as shown in the reaction formula (3) is brought
about, and the layer composed of the organic semiconductor is formed.
When the layer formed of the organic semiconductor is formed by heating,
heat to be applied to the layer composed of the organic semiconductor
precursor, which is only required to have such a temperature that the
precursor is converted into the organic semiconductor, is preferably heat
at 100° C. or higher and 250° C. or lower. In addition,
when the layer composed of the organic semiconductor is formed by
irradiation with light, the wavelength of light with which the layer
composed of the organic semiconductor precursor is irradiated, is only
required to fall within an absorption wavelength region of the organic
semiconductor precursor, and falls within a wavelength region of
preferably 190 nm or more and 350 nm or less, or more preferably 220 nm
or more and 280 nm or less. When the wavelength falls within the above
region, the precursor can be efficiently converted into the organic
semiconductor. A light source is selected from, for example, a tungsten
lamp, a halogen lamp, a metal halide lamp, a sodium lamp, a xenon lamp, a
high-pressure mercury lamp, a low-pressure mercury lamp, and various
laser light beams. A method of irradiating the layer with light is not
particularly limited as long as the organic semiconductor precursor is
changed to the organic semiconductor, but a method of directly
irradiating the organic semiconductor precursor with light is desirable
in order that a photoreaction may be more effectively performed. When
heat generated by the irradiation with light is applied to the organic
semiconductor precursor, the heat is preferably cut off with a heat
absorbing filter or the like. In addition, the organic semiconductor can
be patterned by irradiating the layer with light through a mask. It is
more preferable that light and heat be simultaneously applied to the
layer composed of the organic semiconductor precursor in order that an
excellent crystallized film of the organic semiconductor may be obtained.
In this case, heat is applied by heating the base body from the outside
of the body. Any method may be employed as a heating method, but a
preferable method is a method involving heating the base body on a hot
plate, or in an oven with hot air circulation or a vacuum oven. Of those,
in the present invention, a method involving heating the base body on a
hot plate is more preferable. While the optimum temperature at which the
base body is heated varies depending on the type of organic semiconductor
precursor, the base body is preferably heated in the temperature region
of 50° C. or higher and 180° C. or lower in consideration
of, for example, an influence on the peripheral part of the layer.

[0148] As describe above, the concept of the term "or" includes "and", and
the heat and irradiation with light may be performed simultaneously. When
light and heat are simultaneously applied to the layer, the time period
for which light and heat are simultaneously applied to the layer varies
depending on, for example, the thickness and material of the layer to a
large extent, so the time period cannot be uniquely determined. In
general, however, it becomes difficult for light to permeate into a deep
portion of the crystallized film of the organic semiconductor as the film
grows, so the time period for which light energy and heat energy are
simultaneously applied to the layer is preferably 1 second or longer and
30 minutes or shorter. In such a manner, light can be effectively
utilized in converting the organic semiconductor precursor into the
organic semiconductor. The time period for which light energy and heat
energy are simultaneously applied to the layer is more preferably minute
or longer and 15 minutes or shorter. In addition, in order to obtain a
more stable crystallized film, only heat energy may be further applied
after simultaneously applying light energy and heat energy.

[0149] The layer formed of the organic semiconductor obtained through
those operations has a thickness of preferably 10 nm or more and 500 nm
or less, or more preferably 20 nm or more and 200 nm or less. The
thickness can be measured with, for example, a surface roughness meter or
a level difference meter.

[0150]FIG. 2 shows the schematic sectional view of an organic field
effect transistor when the organic field effect transistor is obtained
through the above steps. The field effect transistor shown in FIG. 2 is
made up of a gate electrode 7, an insulating layer 8, a layer 9 composed
of an organic semiconductor, a source electrode 10, and a drain electrode
11. Description is given here on the assumption that a base body is
comprised of the gate electrode 7 and the insulating layer 8.

[0151] The gate electrode 7, the source electrode 10, and the drain
electrode 11 are not particularly limited as long as they are made of
conductive materials. Examples of the materials include: platinum, gold,
silver, nickel, chromium, copper, iron, tin, antimonial lead, tantalum,
indium, aluminum, zinc, magnesium, and alloys of those metals; conductive
metal oxides such as an indium-tin oxide; and inorganic and organic
semiconductors with increased conductivity through doping and the like,
such as a silicon single crystal, polysilicon, amorphous silicon,
germanium, graphite, polyacetylene, polyparaphenylene, polythiophene,
polypyrrole, polyaniline, polythienylenevinylene, and
polyparaphenylenevinylene. Examples of a method of producing an electrode
include a sputtering method, an evaporation method, a printing method
from a solution or a paste, an inkjet method, and a dipping method. In
addition, an electrode material is preferably any of the above materials
that have low electrical resistance at a contact surface with the
semiconductor layer.

[0152] The insulating layer 8 is not limited as long as the layer formed
of the organic semiconductor can be uniformly applied to the layer, but
the insulating layer is preferably one having a high dielectric constant
and low conductivity. Examples of a material for the insulating layer
include: inorganic oxides and nitrides such as silicon oxide, silicon
nitride, aluminum oxide, titanium oxide, and tantalum oxide;
polyacrylate; polymethacrylate; polyethylene terephthalate; polyimide;
and polyether. Of those materials for the insulting layer, a material
having high surface smoothness is preferable.

[0153] A field effect transistor structure in the present invention may be
any one of a top contact electrode type, a bottom contact electrode type,
and a top gate electrode type. In addition, the structure is not limited
to a horizontal type structure, and may be a vertical type structure
(structure in which one of a source electrode and a drain electrode is
present on the surface of an organic semiconductor layer on the side of a
base material and the other is present on the surface of the organic
semiconductor layer on the side opposite to the base material).

EXAMPLES

Synthesis Example 1

[0154] Step (1)

[0155] 2,4-pentanedione (205.4 ml, 2.0 mol), acetone (100 ml), n-butyl
bromide (54 ml, 0.5 mol), and potassium carbonate (34.55 g, 0.25 mol)
were fed into a reaction vessel, air in the vessel was replaced with
nitrogen, and reflux was carried out for 48 hours. The resultant solid
was filtered out, and the solvent was distilled off by means of an
evaporator. After that, unreacted 2,4-pentanedione was distilled off
under reduced pressure by means of a diaphragm. Then, the remainder was
distilled in a vacuum to yield 3-n-butyl 2,4-petanedione (43.25 g, 55%
yield).

[0156] Step (2)

[0157] Benzyl acetoacetate (97 ml, 560 mmol) and acetic acid (81 ml) were
fed into a reaction vessel. Then, a solution of sodium nitrite (37.8 g)
in water (115 ml) was dropwise added into the mixture at 10° C. or
lower. After the dropping, the mixture was stirred for 3 hours at room
temperature. A solution of 3-n-butyl 2,4-pentanedione (43.16 g, 280 mmol)
obtained in Step (1) in acetic acid (45 ml), a mixture of zinc powder
(36.6 g) and sodium acetate (25.9 g), and the above solution were fed
into another vessel at 60° C. or lower, and was stirred at
80° C. for 1 hour. After that, the reaction solution was poured
into ice water (1.12 L), and the resultant precipitate was filtered and
washed with water. The precipitate was dissolved in chloroform and washed
with water, a saturated aqueous solution of sodium bicarbonate, and a
saturated salt solution. The organic layer was dried over anhydrous
sodium sulfate, concentrated, and distilled under reduced pressure by
means of a diaphragm to remove an excess liquid. The remainder was
purified by means of silica gel column chromatograghy (EtOAc/Hexane) and
recrystallized (MeOH) to yield 4-n-butyl-3,5-dimethylpyrrole benzylester
(22.92 g, 24% yield).

[0158] Step (3)

[0159] Acetic acid (200 ml) and acetic anhydride (3.09 ml) were fed into a
reaction vessel. 4-n-butyl-3,5-dimethylpyrrole benzylester (8.56 g, 30
mmol) was dissolved into the mixture, and then lead tetraacetate (15.38
g, 31.5 mmol) was slowly added to the solution. After the mixture had
been stirred for 2 hours, and the reaction solution was poured into the
ice water. The produced precipitate was filtered, and was thoroughly
washed with water. The precipitate was dissolved into chloroform, and was
washed with water, a saturated aqueous solution of sodium bicarbonate,
and a saturated salt solution. The organic layer was dried over anhydrous
sodium sulfate, concentrated under reduced pressure, and subjected to
trituration with hexane to yield benzyl
5-acetoxymethyl-4-n-butyl-3-methylpyrrole-2-carboxylate (8.93 g, 87%
yield).

[0160] Step (4)

[0161] Air in a reaction vessel was replaced with nitrogen, and
1-nitropropane (8.93 ml, 100 mmol) and dehydrated tetrahydrofuran
(dry-THF) (50 ml) were added to the vessel. Then,
1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) (1.5 ml, 10 mmol) was added to
the mixture. After that, propionaldehyde (4.68 ml, 100 mmol) was added to
the mixture while being was cooled on an ice bath. After the mixture had
been stirred at room temperature for 10 hours, ethyl acetate (100 ml) was
added to the mixture, and was washed with dilute hydrochloric acid,
water, and a saturated salt solution, and the organic layer was dried
over anhydrous sodium sulfate and concentrated under reduced pressure,
whereby 4-hydroxy-3-nitrohexane was obtained (12.33 g, 84% yield).

[0162] Step (5)

[0163] 4-hydroxy-3-nitrohexane (14.7 g, 100 mmol), acetic anhydride (14.8
ml, 157.3 mmol), chloroform (50 ml), and several drops of concentrated
sulfuric acid were fed into a reaction vessel, and the mixture was
stirred at room temperature for 10 hours. After the completion of the
reaction, chloroform (50 ml) was added, and washed with water, a 5%
aqueous solution of sodium bicarbonate, and a saturated salt solution.
The organic layer was dried over anhydrous sodium sulfate and
concentrated under reduced pressure to yield 4-acetoxy-3-nitrohexane
(16.3 g, 86% yield).

[0164] Step (6)

[0165] After 4-acetoxy-3-nitrohexane (11.34 g, 60 mmol) had been added to
a reaction vessel, air in the vessel was replaced with nitrogen, and
dry-THF (150 ml) and ethyl isocyanoacetate (7.28 ml, 66 mmol) were added.
Then, DBU (20.76 ml, 144 mmol) was slowly dropwise added while being
cooled on an ice bath, and stirred at room temperature for 12 hours.
After the completion of the reaction, 1 N hydrochloric acid was added,
and extracted with chloroform, and the extract was washed with water and
a saturated salt solution. The organic layer was dried over anhydrous
sodium sulfate and concentrated under reduced pressure. After that, the
concentrated product was purified by means of silica gel column
chromatography to yield ethyl 3,4-diethylpyrrole-2-carboxylate (10.97 g,
94% yield).

[0166] Step (7)

[0167] Ethyl 3,4-diethylpyrrole-2-carboxylate obtained in Step (6) (2.056
g, 10.53 mmol), ethylene glycol (100 ml), and potassium hydroxide (3.5 g)
were placed in a light-shielded reaction vessel equipped with a reflux
condenser. Then, the inside of the reaction vessel was replaced with
nitrogen and the mixture was stirred at 160° C. for 2.5 hours.
After that, the reaction solution cooled to room temperature was poured
into ice water, and extracted with ethyl acetate, and the extract was
washed with an aqueous solution of sodium bicarbonate, water, and a
saturated salt solution. The organic layer was dried over anhydrous
sodium sulfate and concentrated under reduced pressure, thereby to obtain
3,4-diethylpyrrole. Again, 3,4-diethylpyrrole obtained by this reaction,
benzyl-5-acetoxymethyl-4-n-butyl-3-methylpyrrole-2-carboxylate obtained
in Step (3) (7.21 g, 21 mmol), acetic acid (10 ml), and ethanol (150 ml)
were fed into a light-shielded reaction vessel equipped with a reflux
condenser, and was refluxed for 18 hours. After the reflux, the resultant
was cooled to room temperature, ethanol (50 ml) was added, and was left
standing at 0° C. for 5 hours. The precipitated crystal was
filtered out and thoroughly washed with ethanol to yield
2,5-bis(5-benzylcarbonyl-3-n-butyl-4-methyl-2-pyrroylmethyl)-3,4-dimethyl-
-1H-pyrrole (5.25 g, 72% yield).

[0168] Step (8)

[0169] Palladium carbon (Pd/C) (0.5 g) and dry-THF (20 ml) were fed into a
three-necked flask, and air in the flask was replaced with hydrogen, and
stirring was carried out for 30 minutes. A solution prepared by
dissolving
2,5-bis(5-benzylcarbonyl-3-n-butyl-4-methyl-2-pyrroylmethyl)-3,4-dimethyl-
-1H-pyrrole (2.09 g, 3.03 mmol) in dry-THF (30 ml) was slowly dropwise
added into the mixture, and was stirred at room temperature overnight.
After the stirring, the solution was subjected to Celite filtration. The
filtrate was concentrated under reduced pressure, shielded from light,
and cooled on an ice bath in a nitrogen atmosphere. Trifluoro acetate
(TFA) (5 ml) was dropwise added, and was stirred for 10 minutes. After
that, trimethyl orthoformate (CH(OMe)3) (10 ml) was slowly dropwise
added, and was stirred at 0° C. for 1 hour. After the solution had
been neutralized with 1 M NaOH (which had been diluted with a solution of
MeOH/H2O=1/1), the resultant was poured into ice water. As a result,
a brown solid precipitated. The solid was filtered out, washed with
water, and rinsed with hexane to yield
2,5-bis(5-formyl-3-n-butyl-4-methyl-2-pyrroylmethyl)-3,4-diethyl-1H-pyrro-
le (1.94 g, 60% yield).

[0170] Step (9)

[0171] 1,4-cyclohexadiene (73.77 ml, 0.78 mmol) was placed in a
three-necked flask, stirred, and cooled to -45° C. A solution of
bromine (122.5 g, 0.77 mmol) in hexane (350 ml) was slowly dropwise added
to the flask over 4 hours or longer. After the completion of the
dropping, the reaction solution was returned to room temperature and
filtrated, and the filtrate was concentrated and dried under reduced
pressure, whereby 4,5-dibromo-1-cyclohexene was obtained (146.5 g, 79%).

[0172] Step (10)

[0173] The compound obtained in Step (9) (80.5 g, 338 mmol), water (500
ml), acetone (250 ml), and N-methylmorpholine (45.5 g, 389 mmol) were
placed in a reaction vessel, and was stirred. OsO4 (1 g) was added
to the mixture, and was vigorously stirred for 24 hours. After the
completion of the reaction, a suspension of NaHSO3 (50 g) and
Florisil (250 g) in water (100 ml) was added to the reaction solution,
and was stirred for 10 minutes. After that, insoluble matter was removed
by celite filtration, and 5% HCl was added to the filtrate until the pH
of the filtrate became 3. Upon confirming that the pH had reached 3, and
acetone was removed under reduced pressure. Organic matter was extracted
from the remainder with ethyl acetate, dried over sodium sulfate, and
concentrated under reduced pressure. The precipitated crystals were
filtrated, and was then recrystallized with methylene chloride, whereby
4,5-dibromo-1,2-cyclohexanediol was obtained (64.6 g, 70%).

[0174] Step (11)

[0175] The compound obtained in Step (10) (20.6 g, 75.62 mmol) was placed
in a reaction vessel, and air in the vessel was replaced with nitrogen.
2,2-dimethoxypropane (12.92 ml) and p-toluenesulfonic acid (0.9 g) were
added to the vessel, and the mixture was stirred for 3 hours. After the
completion of the reaction had been confirmed, the mixture was filtrated
through activated alumina, and the filtrate was concentrated under
reduced pressure, whereby
5,6-dibromo-2,2-dimethylhexahydro-1,3-benzodioxol was obtained (17.1 g,
72%).

[0176] Step (12)

[0177] The compound obtained in Step (11) was placed in a reaction vessel,
and air in the vessel was replaced with nitrogen. After that, the
compound was dissolved in dehydrated toluene (116 ml). Distilled DBU (6.0
ml, 40.1 mmol) was added to the solution, and the mixture was refluxed
for 6 hours. After the reaction product had been filtrated, sodium
hydrogen carbonate was added to the filtrate, and the organic layer was
dried over magnesium sulfate, whereby
2,2-dimethyl-3a,7a-dihydrobenzo[1.3]dioxol was obtained. The compound was
used in the next reaction without being further purified.

[0178] Step (13)

[0179] Trans-1,2-bis(phenylsulfonyl)ethylene (1.37 g, 4.45 mmol) was added
to a solution of the compound obtained in Step (12) in toluene, and air
in a vessel containing the mixture was replaced with nitrogen. After
having been refluxed for 8 hours, the mixture was concentrated under
reduced pressure. The resultant reaction product was purified by silica
gel chromatography (50% EtOAc/Hexane), whereby
10,11-bis(phenylsulfonyl)-4,4-dimethyl-3,5-dioxa-tricyclo[5.2.2.02.6-
]undec-8-ene was obtained (2.0 g, 98%).

[0180] Step (14)

[0181] The compound obtained in Step (13) (4.0 g, 8.7 mmol) was placed in
a reaction vessel, and air in the vessel was replaced with nitrogen.
After that, the compound was dissolved in tetrahydrofuran (24 ml). Ethyl
isocyanoacetate (1.3 ml, 12.2 mmol) and 1M t-BuOK (tetrahydrofuran
solution) (21.7 ml, 21.7 mmol) were added to the solution on an ice bath.
Thereafter, the mixture was stirred at room temperature for 18 hours. A
10% HCl aqueous solution (24.4 ml) and 160 ml of water were added to the
reaction solution, and then the mixture was extracted with ethyl acetate,
washed with a saturated salt solution, dried over anhydrous sodium
sulfate, and concentrated under reduced pressure. The resultant reaction
product was purified by silica gel chromatography, whereby a target
product represented by a general formula (a) was obtained (2.4 g, 95%).

##STR00092##

[0182] Step (15)

[0183] The compound obtained in Step (14) (1 g, 3.45 mmol), ethylene
glycol (50 ml), and potassium hydroxide (0.8 g) were placed in a reaction
vessel, and air in the vessel was replaced with nitrogen. After that, the
mixture was stirred at 175° C. for 5 hours. Thereafter, the
reaction solution was returned to room temperature and poured into water,
and was then extracted with ethyl acetate, washed with water and a
saturated salt solution, and purified by silica gel chromatography,
whereby a target product represented by a general formula (b) was
obtained (0.52 g, 70%).

##STR00093##

[0184] Step (16)

[0185] Methylene chloride (300 ml) and trichloroacetic acid (8.43 g) were
placed into a reaction vessel, and air in the vessel was replaced with
nitrogen. A liquid prepared by dissolving the compound synthesized in
Step (8) (0.79 g, 1.7 mmol) and the compound synthesized in Step (15)
(0.37 g, 1.7 mmol) in methylene chloride (125 ml) was dropwise added to
the mixture over 15 minutes. After that, the mixture was stirred at room
temperature for 20 hours, and was then neutralized with triethylamine.
Chloranil was added to the neutralized product, and the mixture was
stirred for 2.5 hours. The reaction solution was poured into water, and
the mixture was extracted with methylene chloride, washed with a
saturated sodium bicarbonate solution and water, dried over anhydrous
sodium sulfate, concentrated under reduced pressure, and purified by
alumina column chromatography, whereby a compound represented by a
general formula (c) was obtained (0.18 g, 16%).

##STR00094##

[0186] Step (17)

[0187] The compound obtained in Step (16) was placed in a reaction vessel
and dissolved in tetrahydrofuran, and 6N HCl was added to the solution.
After that, the mixture was stirred at room temperature. Thereafter, the
reaction solution was poured into water, and the mixture was extracted
with ethyl acetate, washed with water, dried over anhydrous sodium
sulfate, and concentrated under reduced pressure, whereby a compound
represented by a general formula (d) was obtained.

##STR00095##

[0188] Step (18)

[0189] Air in a reaction vessel was replaced with nitrogen, and dimethyl
sulfoxide (0.8 ml) and methylene chloride (2.1 ml) were added to the
vessel. After that, trifluoroacetic anhydride (1.0 ml) was dropwise added
to the mixture at -60° C., and was stirred for 10 minutes.
Thereafter, a solution of the compound represented by the general formula
(d) obtained in Step (17) (39 mg, 0.063mmol) in dimethyl sulfoxide was
dropwise added to the mixture at -60° C., and was stirred for 1.5
hours. Then, triethylamine (2.5 ml) was added to the mixture at
-60° C., and was stirred for an additional 1.5 hours. After that,
the reaction solution was returned to room temperature and poured into a
10% HCl aqueous solution, and the mixture was extracted with methylene
chloride, washed with water, dried over anhydrous sodium sulfate,
concentrated under reduced pressure, and purified by silica gel
chromatography, whereby a compound represented by a general formula (e)
was obtained (24 mg, 62% yield). 1H NMR (CDCl3) δ=10.13,
7.39, 6.14, 4.15, 4.01, 3.71, 2.31, 1.90, 1.73, 1.11, -3.89

[0190] Infrared absorption spectrum (ATR) cm-1: 1,739 (CO)

[0191] Mass spectrum (MALDI-TOF-MS) m/z: 556.358, 613.441

##STR00096##

Synthesis Example 2

[0192] Step (1)

[0193] The compound represented by the general formula (a) synthesized in
Step (14) of Synthesis Example 1 (0.29 g, 1.0 mmol) was placed in a
reaction vessel, and air in the vessel was replaced with nitrogen. The
compound was dissolved in anhydrous tetrahydrofuran (5.0 ml), and the
reaction vessel was immersed in an ice bath. Lithium aluminum hydride
(0.11 g, 3.0 mmol) was added to the solution, the ice bath was removed,
and the mixture was stirred at room temperature for 1 hour. After the
completion of the reduction, a saturated salt solution (20 ml) was added
to the mixture, insoluble matter was subjected to celite filtration, and
the remainder was extracted with chloroform and dried over anhydrous
sodium sulfate. p-toluenesulfonic acid (0.08 g) was added to the
solution, and the mixture was stirred for 1 day. Further, chloranil (0.22
g, 0.91 mmol) was added to the mixture, and was stirred for an additional
1 day. After the completion of the reaction, the reaction solution was
washed with a 1% sodium thiosulfate aqueous solution and a saturated salt
solution, dried over anhydrous sodium sulfate, concentrated under reduced
pressure, purified by silica gel column chromatography, and
recrystallized, whereby a compound represented by a general formula (f)
was obtained (0.05 g, 21%).

##STR00097##

[0194] Step (2)

[0195] The compound represented by the general formula (f) synthesized in
Step (1) of Synthesis Example 2 was placed into a reaction vessel, and
air in the vessel was replaced with nitrogen. After that, the compound
was dissolved in tetrahydrofuran. A 1M HCl aqueous solution was added in
an amount equal to that of tetrahydrofuran to the solution, and the
mixture was stirred for 4 hours. After the completion of the reaction,
the mixture was extracted with ethyl acetate, washed with water and a
saturated salt solution, dried over anhydrous sodium sulfate,
concentrated under reduced pressure, purified by silica gel
chromatography, and recrystallized, whereby a compound represented by a
general formula (g) was obtained (84%).

##STR00098##

[0196] Step (3)

[0197] Air in a reaction vessel was replaced with nitrogen, and dimethyl
sulfoxide (0.8 ml) and methylene chloride (5.0 ml) were added to the
vessel. After that, trifluoroacetic anhydride (1.2 ml) was dropwise added
to the mixture at -60° C., and was stirred for 10 minutes.
Thereafter, a solution of the compound represented by the general formula
(g) obtained in Step (2) of Synthesis Example 2 (50 mg, 0.067 mmol) in
dimethyl sulfoxide (0.5 ml) was dropwise added to the mixture at
-60° C., and was stirred for 1.5 hours. Then, triethylamine (2.7
ml) was added to the mixture at -60° C., and was stirred for an
additional 1.5 hours. After that, the reaction solution was returned to
room temperature and poured into a 10% HCl aqueous solution, and was
extracted with methylene chloride, washed with water and a saturated salt
solution, dried over anhydrous sodium sulfate, concentrated under reduced
pressure, and triturated with ethyl acetate, whereby a compound
represented by a general formula (h) was obtained (15 mg, 30%).

[0198]1H NMR (CDCl3) δ=9.99, 7.51, 6.20

[0199] Infrared absorption spectrum (ATR) cm.sup.-: 1,728 (CO)

[0200] Mass spectrum (MALDI-TOF-MS) m/z: 510.291 (only the mass of a benzo
body was observed because a carbonyl group was eliminated during
ionization).

##STR00099##

[0201] Step (4)

[0202] The compound represented by the general formula (f) and zinc
acetate were allowed to react with each other, whereby a zinc complex was
obtained. The resultant compound (1.0 g), THF (100 ml), and 1N HCl (100
ml) were mixed, and air in a reaction vessel containing the mixture was
replaced with nitrogen. After that, the mixture was stirred at 65°
C. for 3 hours and returned to room temperature. The reaction solution
was concentrated, and then the concentrate was dissolved in ethanol. The
solution was passed through sodium hydrogen carbonate so as to be
concentrated again. After that, the resultant compound was purified by
silica gel column chromatography, whereby a zinc complex of the compound
represented by the general formula (g) was quantitatively obtained.

[0203] Step (5)

[0204] Air in a reaction vessel was replaced with nitrogen, and dimethyl
sulfoxide (0.93 ml) and methylene chloride (5.4 ml) were added to the
vessel. After that, trifluoroacetic anhydride (1.3 ml) was dropwise added
to the mixture at -60° C., and was stirred for 10 minutes. After
that, a solution of the zinc complex of the compound represented by the
general formula (g) obtained in Step (4) of Synthesis Example 2 (59 mg,
0.072 mmol) in dimethyl sulfoxide (1.0 ml) was dropwise added to the
mixture at -60° C., and was stirred for 1.5 hours. After that,
triethylamine (3.0 ml) was added to the mixture at -60° C., and
was stirred for an additional 1.5 hours. After that, the reaction
solution was returned to room temperature and poured into a 10% aqueous
solution of HCl, and the mixture was extracted with methylene chloride,
washed with water and a saturated salt solution, dried over anhydrous
sodium sulfate, concentrated under reduced pressure, and triturated with
ethyl acetate, whereby a zinc complex of the compound represented by the
general formula (h) was obtained (16 mg, 28%).

[0205]1H NMR (CDCl3) δ=10.17 (4H, m), 7.45 (8H, m), 6.18
(8H, m)

[0206] Infrared absorption spectrum (ATR) cm-1: 1,728 (CO)

[0207] Mass spectrum (MALDI-TOF-MS) m/z: 510.329 (only the mass of a benzo
body was observed because a carbonyl group and zinc as a central metal
were eliminated during ionization).

[0208] Step (6)

[0209] The compound represented by the general formula (h) and copper
acetate were allowed to react with each other, whereby a copper complex
was quantitatively obtained.

[0210] Infrared absorption spectrum (ATR) cm-1: 1,728 (CO)

[0211] Mass spectrum (MALDI-TOF-MS) m/z: 510.303 (only the mass of a benzo
body was observed because a carbonyl group and copper as a central metal
were eliminated during ionization).

Synthesis Example 3

[0212] Step (1)

[0213] Phosphorus pentoxide (17 g, 60 mmol) was placed in a three-necked
flask, and air in the flask was replaced with nitrogen. In the presence
of P2O5, sulfolane distilled under reduced pressure (70 ml) was
placed in the flask. Acetylene dicarboxyamide (5 g, 45 mmol) suspended in
sulfolane was dropwise added to the mixture at 110° C. and 12 Torr
over 30 minutes or more.

[0214] After the completion of the dropping, the temperature of the
reaction liquid was set at 120° C., where produced
dicyanoacetylene was vaporized, and hence, was recovered while being
cooled in a dry ice-acetone bath (0.85 g, 25%).

[0215] Step (2)

[0216] Air in an egg plant flask containing dicyanoacetylene (0.38 g, 5.0
mmol) was replaced with nitrogen, and toluene was added to dissolve
dicyanoacetylene. 2,2-dimethyl-3a,7a-dihydrobenzo[1.3]dioxol (0.31 g, 2.0
mmol) was added to the solution, and was stirred at room temperature
overnight. After that, the resultant was washed with water and a
saturated salt solution, dried over anhydrous sodium sulfate,
concentrated under reduced pressure, and purified by silica gel column
chromatography, whereby a compound represented by a general formula (i)
was obtained (0.46 g, 40%).

##STR00100##

[0217] Step (3)

[0218] Magnesium (3.1 mg), dehydrated butanol (4.4 ml), and a slight
amount of iodine were placed in a reaction vessel whose inside had been
replaced with nitrogen, and stirred at 120° C. for 3 hours. The
resultant solution (1.2 ml) was added to a reaction vessel which
contained the compound represented by the general formula (i) obtained in
Step (2) of Synthesis Example 3 (20 mg, 0.08 mmol) and whose inside had
been replaced with nitrogen, and the mixture was stirred at 120°
C. for 2 days. The reaction solution was poured into a solution
containing water and methanol in a ratio of 1 : 1, and was extracted with
chloroform. The organic layer was washed with water and a saturated salt
solution, dried over anhydrous sodium sulfate, concentrated under reduced
pressure, and separated by alumina column chromatography, whereby a
compound represented by a general formula (j) was obtained (7% yield).

##STR00101##

[0219] Step (4)

[0220] The compound represented by the general formula (j) obtained in
Step (3) of Synthesis Example 3 is placed in a reaction vessel, air in
the vessel is replaced with nitrogen, and the compound is dissolved in
tetrahydrofuran. 1N hydrochloric acid is added to the solution, and the
mixture is stirred at room temperature. After the completion of the
reaction, the mixture is washed with a saturated salt solution, and the
organic layer is dried over anhydrous sodium sulfate, concentrated under
reduced pressure, purified by silica gel column chromatography, and
recrystallized, whereby a compound represented by a general formula (k)
can be obtained.

##STR00102##

[0221] Step (5)

[0222] Air in a reaction vessel is replaced with nitrogen, and dimethyl
sulfoxide and methylene chloride are added to the vessel. After that,
trifluoroacetic anhydride is dropwise added to the mixture at -60°
C., and stirred for 10 minutes. After that, a solution of the compound
represented by the general formula (k) obtained in Step (4) of Synthesis
Example 3 in dimethyl sulfoxide is dropwise added to the mixture at
-60° C., and stirred for 1.5 hours. Thereafter, triethylamine is
added to the mixture at -60° C., and stirred for an additional 1.5
hours. Then, the reaction solution is returned to room temperature,
poured into a 10% HCl aqueous solution, extracted with methylene
chloride, washed with water and a saturated salt solution, dried over
anhydrous sodium sulfate, concentrated under reduced pressure, and
purified by silica gel chromatography, whereby a compound represented by
a general formula (1) can be obtained.

##STR00103##

Synthesis Example 4

[0223] A reaction solution containing pentacene (0.46 g, 1.6 mmol) and
thiophosgene (2 ml) was subjected to reaction at 65° C. for 6
hours. The reaction solution was cooled to room temperature, and
dichloromethane (2 ml) was added to the reaction solution. After that,
the mixture was filtrated so that unreacted pentacene was removed, and
the filtrate was concentrated under reduced pressure. After the
concentration, 40 ml of toluene were added to the concentrate, and the
mixture was concentrated under reduced pressure so that unreacted
thiophosgene was removed. The resultant product was purified by silica
gel column chromatography, whereby a compound represented by a general
formula (16) was obtained (40% yield).

##STR00104##

[0224] Preparation of Resin Solution a

[0225] Resin Solution a was prepared by dissolving 1.0 g of commercially
available flaky methyl silsesquioxane (MSQ) (manufactured by SHOWA DENKO
K.K.; trade name: GR650) in a mixed solvent composed of 49.5 g of ethanol
and 49.5 g of 1-butanol.

[0226] Preparation of Resin Solution b

[0227] 1.0 g of methyltrimethoxysilane was completely dissolved in a mixed
solvent composed of 49.5 g of ethanol and 49.5 g of 1-butanol. 0.83 g of
distilled water and 0.05 g of formic acid were added to the solution, and
stirred at room temperature for 48 hours, whereby Silica Sol (Resin
Solution) b was prepared.

Example 1

[0228] FIG. 1 shows the structure of a top electrode type field effect
transistor in this example.

[0229] First, a highly doped N-type silicon substrate was defined as the
gate electrode 1. A silicon oxide film having a thickness of 500 nm
(5,000 {acute over (Å)}) obtained by thermally oxidizing the surface
layer of the silicon substrate was defined as the gate insulating layer
2. Next, Resin Solution a was applied to the surface of the insulating
layer by a spin coating method (at the number of revolutions of 5,000
rpm). Next, the coating film was transferred to a hot plate, and was
heated at 100° C. for 5 minutes and at 220° C. for 30
minutes. Thus, the A layer 3 (polysiloxane layer) was formed.

[0230] Next, a 1.0 wt % solution of the compound represented by the
general formula (e) synthesized in Synthesis Example 1 in chloroform was
applied onto the substrate on which the A layer 3 had been thus formed by
a spin coating method at the number of revolutions of 900 rpm. Thus, a
coating film was formed. Further, the substrate on which the coating film
had been thus formed was mounted on a hot plate set at 150° C.,
and was irradiated with light from a metal halide lamp manufactured by
NIPPON P.I. CO., LTD. (PCS-UMX250) through a heat absorbing filter and a
blue filter for 5 minutes. Thus, the B layer 6 (organic semiconductor
layer) was formed.

[0231] Au was vapor-deposited onto the B layer 6 by using a mask, whereby
the source electrode 4 and the drain electrode 5 were formed. The
conditions under which the electrodes were produced were as follows: a
degree of vacuum in a vacuum device chamber was 1×10-6 torr,
and the temperature of the substrate was room temperature. The electrodes
thus obtained each had a thickness of 100 nm.

[0232] A field effect transistor having a channel length L of 50 μm and
a channel width W of 3 mm was produced by the foregoing procedure. The
Vd-Id and Vg-Id curves of the produced transistor
were measured with a parameter analyzer 4156C (trade name) manufactured
by Agilent.

[0233] A mobility μ (cm2/Vs) of the transistor was calculated in
accordance with the following equation (1).

Id=μ(CiW/2L)×(Vg-Vth)2 (Eq. 1)

[0234] In the equation, Ci represents the electrostatic capacity of the
gate insulating layer per unit area (F/cm2), W and L represent the
channel width (mm) and the channel length (μm) shown in the example,
respectively, and Id, Vg, and Vth represent a drain
current (A), a gate voltage (V), and a threshold voltage (V),
respectively. In addition, a ratio of Id at Vg of -80 V to
Id at Vg of 0 V at Vd of -80 V was defined as an on/off
ratio. The field effect mobility calculated from the obtained results was
1.8 x 10-3 cm2/Vs. In addition, the on/off ratio was
3.1×103. In addition, the substrate of the transistor was
subjected to CuKa X-ray diffraction measurement. As a result, a
diffraction peak was observed, and it was confirmed that the substrate
had satisfactory crystallinity.

Example 2

[0235] A highly doped N-type silicon substrate was defined as a gate
electrode. A silicon oxide film having a thickness of 500 nm (5,000
{acute over (Å)}) obtained by thermally oxidizing the surface layer
of the silicon substrate was defined as a gate insulating layer. Next, a
1.0 wt % solution of the compound represented by the general formula (e)
synthesized in Synthesis Example 1 in chloroform was applied onto the
substrate by a spin coating method at the number of revolutions of 900
rpm. Thus, a coating film was formed. Further, the substrate on which the
coating film had been thus formed was mounted on a hot plate set at
150° C., and was irradiated with light from a metal halide lamp
manufactured by NIPPON P.I. CO., LTD. (PCS-UMX250) through a heat
absorbing filter and a blue filter for 5 minutes. Thus, an organic
semiconductor layer was formed.

[0236] Au was vapor-deposited onto the organic semiconductor layer by
using a mask, whereby a source electrode and a drain electrode were
formed. The conditions under which the electrodes were produced were as
follows: a degree of vacuum in a vacuum device chamber was
1×10-6 torr, and the temperature of the substrate was room
temperature.

[0237] The electrodes thus obtained each had a thickness of 100 nm. A
field effect transistor having a channel length L of 50 μm and a
channel width W of 3 mm was produced by the foregoing procedure, and was
evaluated for its electrical characteristics in the same manner as in
Example 1. The transistor had a field effect mobility of
1.0×10-5 cm2/Vs. In addition, the transistor had an
on/off ratio of 3.6×102.

Example 3

[0238] A highly doped N-type silicon substrate was defined as a gate
electrode. A silicon oxide film having a thickness of 500 nm (5,000
{acute over (Å)}) obtained by thermally oxidizing the surface layer
of the silicon substrate was defined as a gate insulating layer. Next, a
1.0 wt % solution of the compound represented by the general formula (16)
synthesized in Synthesis Example 4 in chloroform was applied onto the
substrate by a spin coating method at the number of revolutions of 1,000
rpm. Thus, a coating film was formed. Further, the substrate on which the
coating film had been thus formed was mounted on a hot plate set at
120° C., and was irradiated with light from a UV light source
manufactured by HOYA-SCHOTT (EX250) through a heat absorbing filter for 1
minute. Thus, an organic semiconductor layer was formed. Au was
vapor-deposited onto the organic semiconductor layer by using a mask,
whereby a source electrode and a drain electrode were formed. The
conditions under which the electrodes were produced were as follows: a
degree of vacuum in a vacuum device chamber was 1×10-6 torr,
and the temperature of the substrate was room temperature. The electrodes
thus obtained each had a thickness of 100 nm. A field effect transistor
having a channel length L of 50 μm and a channel width W of 3 mm was
produced by the foregoing procedure. The Vd-Id and
Vg-Id curves of the produced transistor were measured with a
parameter analyzer 4156C (trade name) manufactured by Agilent.

[0239] The mobility μ (cm2/Vs) of the transistor was calculated in
accordance with the following equation (1).

Id=μ(CiW/2L)×(Vg-Vth)2 (Eq. 2)

[0240] In the equation, Ci represents the electrostatic capacity of the
gate insulating layer per unit area (F/cm2), W and L represent the
channel width (mm) and the channel length (μm) shown in the example,
respectively, and Id, Vg, and Vth represent a drain
current (A), a gate voltage (V), and a threshold voltage (V),
respectively. In addition, a ratio Id at Vg of -80 V to Id
at Vg of 0 V at Vd of -80 V was defined as an on/off ratio. The
field effect mobility calculated from the obtained results and the on/off
ratio are shown in Table 1.

Example 4

[0241] A highly doped N-type silicon substrate was defined as a gate
electrode. A silicon oxide film having a thickness of 500 nm (5,000
{acute over (Å)}) obtained by thermally oxidizing the surface layer
of the silicon substrate was defined as a gate insulating layer. Next,
the compound represented by the general formula (16) synthesized in
Synthesis Example 4 and ethanol were mixed in a molar ratio
(ethanol/general formula (16)) of 7.8, and a 1.0 wt % solution was
prepared by adding chloroform to the mixture. The solution was applied
onto the substrate by a spin coating method at the number of revolutions
of 1,000 rpm. Thus, a coating film was formed. Further, the substrate on
which the coating film had been thus formed was mounted on a hot plate
set at 140° C., and was heated for 30 minutes. Thus, an organic
semiconductor layer was formed. Au was vapor-deposited onto the organic
semiconductor layer by using a mask, whereby a source electrode and a
drain electrode were formed. The conditions under which the electrodes
were produced were as follows: a degree of vacuum in a vacuum device
chamber was 1×10-6 torr, and the temperature of the substrate
was room temperature. The electrodes thus obtained each had a thickness
of 100 nm. A field effect transistor having a channel length L of 50
μm and a channel width W of 3 mm was produced by the foregoing
procedure, and was evaluated for its electrical characteristics. However,
the transistor did not show transistor characteristics. Table 1 shows the
results.

Example 5

[0242] A transistor was produced in the same manner as in Example 4 except
that: the temperature of the hot plate was set at 200° C.; and the
organic semiconductor layer was formed with the time period for which the
substrate was heated changed to 1 minute, and the transistor was
evaluated for its electrical characteristics. Table 1 shows the results.

Example 6

[0243] A highly doped N-type silicon substrate was defined as a gate
electrode. A silicon oxide film having a thickness of 500 nm (5,000
{acute over (Å)}) obtained by thermally oxidizing the surface layer
of the silicon substrate was defined as a gate insulating layer. Next,
the compound represented by the general formula (16) synthesized in
Synthesis Example 4 and ethanol were mixed in a molar ratio
(ethanol/general formula (16)) of 7.8, and a 1.0 wt % solution was
prepared by adding chloroform to the mixture. The solution was applied
onto the substrate by a spin coating method at the number of revolutions
of 1,000 rpm. Thus, a coating film was formed. Further, the substrate on
which the coating film had been thus formed was irradiated with light
from a UV light source manufactured by HOYA-SCHOTT (EX250) through a heat
absorbing filter at room temperature for 1 minute. Thus, an organic
semiconductor layer was formed. Au was vapor-deposited onto the organic
semiconductor layer by using a mask, whereby a source electrode and a
drain electrode were formed. The conditions under which the electrodes
were produced were as follows: a degree of vacuum in a vacuum device
chamber was 1 x 10-6 torr, and the temperature of the substrate was
room temperature. The electrodes thus obtained each had a thickness of
100 nm. A field effect transistor having a channel length L of 50 μm
and a channel width W of 3 mm was produced by the foregoing procedure,
and was evaluated for its electrical characteristics. Table 1 shows the
results.

Example 7

[0244] A highly doped N-type silicon substrate was defined as a gate
electrode. A silicon oxide film having a thickness of 500 nm (5,000
{acute over (Å)}) obtained by thermally oxidizing the surface layer
of the silicon substrate was defined as a gate insulating layer. Next,
the compound represented by the general formula (16) synthesized in
Synthesis Example 4 and ethanol were mixed in a molar ratio
(ethanol/general formula (16)) of 7.8, and a 1.0 wt % solution was
prepared by adding chloroform to the mixture. The solution was applied
onto the substrate by a spin coating method at the number of revolutions
of 1,000 rpm. Thus, a coating film was formed. Further, the substrate on
which the coating film had been thus formed was mounted on a hot plate
set at 120° C. and irradiated with light from a UV light source
manufactured by HOYA-SCHOTT (EX250) through a heat absorbing filter at
room temperature for 1 minute. Thus, an organic semiconductor layer was
formed. Au was vapor-deposited onto the organic semiconductor layer by
using a mask, whereby a source electrode and a drain electrode were
formed. The conditions under which the electrodes were produced were as
follows: a degree of vacuum in a vacuum device chamber was
1×106 torr, and the temperature of the substrate was room
temperature. The electrodes thus obtained each had a thickness of 100 nm.
A field effect transistor having a channel length L of 50 μm and a
channel width W of 3 mm was produced by the foregoing procedure, and was
evaluated for its electrical characteristics. Table 1 shows the results.

Example 8

[0245] A transistor was produced in the same manner as in Example 7 except
that the temperature of the hot plate was set at 130° C., and the
transistor was evaluated for its electrical characteristics. Table 1
shows the results.

Example 9

[0246] A transistor was produced in the same manner as in Example 7 except
that the temperature of the hot plate was set at 140° C., and the
transistor was evaluated for its electrical characteristics. Table 1
shows the results.

Example 10

[0247] A transistor was produced in the same manner as in Example 7 except
that the temperature of the hot plate was set at 180° C., and the
transistor was evaluated for its electrical characteristics. Table 1
shows the results.

[0248] A 1.0 wt % solution of the compound represented by the general
formula (16) in chloroform was prepared, and was applied onto a substrate
by a spin coating method, whereby a film was formed.

Example 12

[0249] The compound represented by the general formula (16) and ethanol
were mixed in a molar ratio (ethanol/general formula (16)) of 1.6, and a
1.0 wt % solution was prepared by adding chloroform to the mixture. The
solution was applied onto a substrate by a spin coating method, whereby a
film was formed.

Example 13

[0250] A film was formed in the same manner as in Example 12 except that
the molar ratio was changed to 7.8.

Example 14

[0251] The compound represented by the general formula (16) and ethanol
were mixed in a molar ratio (ethanol/general formula (16)) of 5.7, and a
1.0 wt % solution was prepared by adding chloroform to the mixture. The
solution was applied onto a substrate by a spin coating method, whereby a
film was formed.

Example 15

[0252] A film was formed in the same manner as in Example 14 except that
the molar ratio was changed to 11.3.

Example 16

[0253] A film was formed in the same manner as in Example 14 except that
the molar ratio was changed to 28.3.

Example 17

[0254] The compound represented by the general formula (16) and isopropyl
alcohol were mixed in a molar ratio (isopropyl alcohol/general formula
(16)) of 5.9, and a 1.0 wt % solution was prepared by adding chloroform
to the mixture. The solution was applied onto a substrate by a spin
coating method, whereby a film was formed.

Example 18

[0255] The compound represented by the general formula (16) and
acetonitrile were mixed in a molar ratio (acetonitrile/general formula
(16)) of 8.7, and a 1.0 wt % solution was prepared by adding chloroform
to the mixture. The solution was applied onto a substrate by a spin
coating method, whereby a film was formed.

Example 19

[0256] A 1.0 wt % solution of the compound represented by the general
formula (16) in toluene was prepared, and was applied onto a substrate by
a spin coating method, whereby a film was formed.

Example 20

[0257] The compound represented by the general formula (16) and ethanol
were mixed in a molar ratio (ethanol/general formula (16)) of 6.7, and a
1.0 wt % solution was prepared by adding toluene to the mixture. The
solution was applied onto a substrate by a spin coating method, whereby a
film was formed.

Example 21

[0258] The compound represented by the general formula (16) and 1-butanol
were mixed in a molar ratio (1-butanol/general formula (16)) of 4.2, and
a 1.0 wt % solution was prepared by adding toluene to the mixture. The
solution was applied onto a substrate by a spin coating method, whereby a
film was formed.

Example 22

[0259] The compound represented by the general formula (16) and toluene
were mixed in a molar ratio (toluene/general formula (16)) of 7.0, and a
1.0-wt % solution was prepared by adding chloroform to the mixture. The
solution was applied onto a substrate by a spin coating method, whereby a
film was formed.

[0260] Films in Examples 11 to 22 each produced on a substrate 1.7 cm by
1.8 cm in size were compared with one another, and the average value of
five 1 mm square points on one substrate was evaluated on the basis of
the following three stages: A, B, and C. Table 2 shows the results.

[0261] (Evaluation for film quality) [0262] A: The average number of
pinholes is less than 15, and the average diameter of the pinholes is
less than 100 μm. [0263] B: The average number of pinholes is 15 or
more and less than 50, and the average diameter of the pinholes is less
than 100 μm. [0264] C: The average number of pinholes is 50 or more,
or the average diameter of the pinholes is 100 μm or more.

[0265] The compound represented by the general formula (e) was dissolved
in deuterated chloroform, and the 1H-NMR of the compound was
measured, whereby it was confirmed that the compound had a structure
represented by the general formula (e). The sample after the measurement
was irradiated with light from a metal halide lamp for 10 minutes. After
that, the 1H-NMR of the sample was measured, whereby it was
confirmed that the sample was changed to a benzo body represented by a
general formula (31) obtained as a result of the elimination of a
carbonyl group from the structure represented by the general formula (e).
FIGS. 4A and 4B show the NMR spectra of the benzo body.

##STR00105##

Example 24

[0266] A solution of a zinc complex of the compound represented by the
general formula (h) in acetone was prepared, and was applied onto a
quartz substrate by a spin coating method at the number of revolutions of
1,000 rpm. The substrate on which a coating film had been thus formed was
irradiated with light from a metal halide lamp in the air at room
temperature for 5 minutes. The fact that the conversion of the compound
into tetrabenzoporphyrin was attained was confirmed by measuring the UV
spectrum of the film. FIG. 3 shows the UV spectrum.

Comparative Example 1

[0267] A 1 wt % solution of a compound represented by the following
general formula (17) in chloroform was prepared, and was applied onto a
quartz substrate by a spin coating method at the number of revolutions of
1,000 rpm. Two substrates on each of which a coating film had been thus
formed were produced. One of the substrates was heated at 250° C.,
and the other was irradiated with light. The heated sample transformed
into pentacene, whereas the sample irradiated with light did not change.

##STR00106##

Comparative Example 2

[0268] Two substrates on each of which a coating film had been formed were
produced in the same manner as in Comparative Example 1 except that a
compound represented by the following general formula (18) was used. One
of the substrates was heated at 200° C., and the other was
irradiated with light from a metal halide lamp manufactured by NIPPON
P.I. CO., LTD. (PCS-UMX250). The heated sample did not change, whereas
the sample irradiated with light transformed into pentacene.

##STR00107##

[0269] While the present invention has been described with reference to
exemplary embodiments, it is to be understood that the invention is not
limited to the disclosed exemplary embodiments. The scope of the
following claims is to be accorded the broadest interpretation so as to
encompass all such modifications and equivalent structures and functions.

[0270] This application claims the benefit of Japanese Patent Application
Nos. 2006-352555, filed Dec. 27, 2006, and 2007-232091 filed on Sep. 6,
2007 which are hereby incorporated by reference herein in their entirety.

Patent applications by Akane Masumoto, Yokohama-Shi JP

Patent applications by Hidemitsu Uno, Matsuyama-Shi JP

Patent applications by Noboru Ono, Matsuyama-Shi JP

Patent applications by Toshihiro Kikuchi, Yokohama-Shi JP

Patent applications by CANON KABUSHIKI KAISHA

Patent applications by EHIME UNIVERSITY

Patent applications in class HAVING ORGANIC SEMICONDUCTIVE COMPONENT

Patent applications in all subclasses HAVING ORGANIC SEMICONDUCTIVE COMPONENT